Methods of disassembling apparel products having cyclodextrin-azobenzene adhesives

ABSTRACT

Embodiments provide methods of disassembling an apparel product. The methods include exposing an adhesive of the apparel product to electromagnetic energy. The adhesive is disposed at least partially between a major component and a minor component of the apparel product. The adhesive includes a polymer having a cyclodextrin moiety bonded to an azobenzene moiety. The major component forms a base portion of the apparel product and is configured to be supported and worn at least partially over a portion of a wearer. The minor component forms a secondary portion configured to be coupled to the major component with the adhesive. The methods include separating the major component from the minor component adjoined by the adhesive.

FIELD

The present disclosure is directed to apparel products, methods ofassembling apparel products, and methods of disassembling apparelproducts.

BACKGROUND

Apparel products are made from various components and each component caninclude different polymer materials. After use, the apparel products areoften found in landfills contributing to waste even though many of theapparel products include materials that still retain structuralintegrity. There has been an increasing effort to recycle, reuse, andreduce products across many industries. However, recycling apparelproducts can be a challenge due to the mix of materials used in thevarious components which must be separated to enable recycling. In theapparel industry, the components of apparel products are often joinedtogether by sewing or other permanent methods and are difficult todisassemble manually or automatically which typically makes recycling ofthe components prohibitively time consuming or costly. Separating thecomponents is possible by manual separation to ensure separating thecomponents while maintaining the integrity of the materials to becollected and recycled. Manual separation cannot keep up with the highvolume of apparel products that are to be recycled and reused and isoften costly. Moreover, forming apparel products that enable streamlinedseparation also needs to be streamlined at large scale.

Therefore, there is a need for apparel products that are easilyassembled and are easy to disassemble and methods of manufacturingand/or disassembling the apparel products.

SUMMARY

In some embodiments, a method of disassembling an apparel product isprovided. The method includes exposing an adhesive of the apparelproduct to electromagnetic energy. The adhesive is disposed at leastpartially between a major component and a minor component of the apparelproduct. The adhesive includes a polymer having a cyclodextrin moietybonded to an azobenzene moiety. The major component forms a base portionof the apparel product and is configured to be supported and worn atleast partially over a portion of a wearer. The minor component forms asecondary portion configured to be coupled to the major component withthe adhesive. The method includes separating the major component fromthe minor component adjoined by the adhesive.

In some embodiments, a method of disassembling an apparel product isprovided. The method includes exposing an adhesive including a polymerhaving a cyclodextrin moiety bonded to an azobenzene moiety to anelectromagnetic energy. The adhesive is disposed at least partiallybetween a major component and a minor component of the apparel product.The composition weakens bonding between the main component and the minorcomponent. The major component forms a base portion of the apparelproduct and is configured to be supported and worn at least partiallyover a portion of a wearer. The minor component forms a secondaryportion configured to be coupled to the major component with theadhesive. The method includes separating the major component from theminor component adjoined by the adhesive. The major component includessynthetic or natural fibers. The major component or minor componentincludes recyclable material.

In some embodiments, a method of disassembling an apparel product isprovided. The method includes exposing a plurality of apparel productsto electromagnetic energy. Each apparel product of the plurality ofapparel products includes an adhesive including a polymer having acyclodextrin moiety bonded to an azobenzene moiety. The adhesive isdisposed at least partially between a major component and a minorcomponent of each apparel product of the plurality of apparel products.Each of the major components form a base portion of the apparel productand is configured to be supported and worn at least partially over aportion of a wearer. Each of the minor components form a secondaryportion configured to be coupled to a respective major component withthe adhesive. The method includes applying a centrifugal force to theplurality of apparel products.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited aspects are attained andcan be understood in detail, a more particular description ofembodiments described herein, briefly summarized above, may be had byreference to the appended drawings.

It is to be noted, however, that the appended drawings illustratetypical embodiments and are therefore not to be considered limiting;other equally effective embodiments are contemplated.

FIG. 1A depicts an apparel product according to some embodiments of thepresent disclosure.

FIG. 1B depicts another apparel product according to some embodiments ofthe present disclosure.

FIG. 2 depicts a portion of a major component coupled to a portion of aminor component according to some embodiments of the present disclosure.

FIG. 3 depicts a process flow diagram of a method for assembling anapparel product according to some embodiments of the present disclosure.

FIG. 4 depicts a process flow diagram of a method for disassembling anapparel product according to some embodiments of the present disclosure.

DETAILED DESCRIPTION

The present disclosure is directed to apparel products, methods ofassembling apparel products, and methods of disassembling apparelproducts. As used herein, an “apparel product,” refers to an articlethat is configured to fit over a portion of a body or is an accessory ofan article configured to fit over the portion of the body. An apparelproduct includes, without limitation, clothing (e.g., shirts, pants,jeans, slacks, skirts, coats, dresses, sweaters, activewear, athletic,aerobic, exercise apparel, swimwear, cycling jerseys or shorts, racesuits, wetsuits, and body suits), footwear (e.g., socks, shoes, boots,loafers), protective apparel (e.g., lab coat, flame retardant clothing),clothing accessories (e.g., hats, masks, scarves, belts, bra straps,side panels, gloves, hosiery, leggings, orthopedic braces, labels,buttons, pockets, purses, tags, security tag, neck ties, bowties)undergarments (e.g., underwear, t-shirts, tank tops, shapewear),compression garments, draped garments (e.g., kits, loincloths, togas,ponchos, cloaks shawls), among others. An apparel product can alsoinclude accessories that can be supported or carried by a wearer, suchas handbags, backpacks, totes, umbrellas, among others.

FIG. 1A depicts an apparel product 100, according to some embodiments.Although the apparel product 100 depicts a long sleeved pull over shirt,any other types, shapes, and uses of articles are also contemplated. Asused herein, an apparel product refers to an article that is formed froma laminate and/or layered material including layers of fabric material,a polymer sheet, or combination thereof. The apparel product can beformed from knitted, woven, or non-woven textile materials. An apparelproduct can be shaped to conform over at least a portion of a humanbody.

The apparel product 100 includes a major component 102 and additionalminor components coupled to the major component 102 and/or coupled toother minor components. As used herein, “components” refer to portionsof an apparel product that can be combined or joined to one another toform the apparel product. A “major component” forms a base portion ofthe apparel product to which one or more minor components are bondedtherewith. A “minor component” includes portions of the apparel productthat can be coupled to one another and/or to the major component to formthe apparel product. As used herein, a minor component includes lessmaterial (e.g., fabric) than a major component. Similarly, majorcomponent includes more material (e.g., fabric) than a minor component.

In some embodiments, the major component 102 can include cotton or apolymer material, such as polyethylene terephthalate (PET) or apolyamide, such as nylon 6,6. In some embodiments, the major component102 can be fleece, such as fleece made up of polyester fibers, polyamidefibers, or combination thereof. As used herein, the term “fleece” refersto one or more layers of strand or threads of textile materials, such aschemical fibers, natural fibers, or combinations thereof. In someembodiments the fleece can be composed of polyester, polyamide,cellulose regeneration and/or lignin fibers, such as natural fibers,wool, cotton, or combinations thereof. The fibers can be short fibers orlong continuous fibers. Each of the minor components can be composed ofthe same or different materials from the major component. In someembodiments, one or more of the minor components can be composed of acontrasting material such as nylon. In some embodiments, the minorcomponents can include a pocket 106 composed of the same or differentmaterial from the major component 102. The pocket 106 can be composed ofa contrasting material such as nylon. The minor components can includelabels 108 which can be composed of polyethylene terephthalate (PET).The labels 108 can include trademarks, logos, branding or designs. Theminor components can include bindings 104 formed along edges of themajor component 102, such as at the cuffs. In some embodiments, thebindings 104 are composed of nylon, spandex, or a combination thereof.

The minor components can further include fasteners 110, such as buttonsor snaps. The fasteners 110 can include a recyclable thermoplastic, suchas polymers such as polyacetal (e.g., commonly referred to as acetal orpolyoxymethylene or POM). In some embodiments, the fasteners 110 includeabout 5 wt. % to about 80 wt. % PET by weight, such as about 10 wt. % toabout 70 wt. %, such as about 20 wt. % to about 60 wt. %, such as about30 wt. % to about 50 wt. %. The minor components can be coupled to themajor component 102 on an outside surface of the major component 102 oron an inside surface of the major component 102. The minor componentscan include hanger loops 112 which can be composed of nylon. The hangerloops 112 are configured to receive a hanger or a hook. Other componentsare also contemplated, such as liners, shells, and design features. Insome embodiments, the major component 102 includes one or morerecyclable materials and one or more of the minor components include oneor more recyclable materials that are different or the same as one ormore of the recyclable materials of the major component 102. In someembodiments, the major component 102 includes one or more recyclablematerials and one or more of the minor components include non-recyclablematerials. In some embodiments, the major component 102 includes one ormore non-recyclable materials and one or more of the minor componentsinclude one or more recyclable materials.

FIG. 1B depicts another apparel product 101, according to someembodiments. The apparel product 101 can include a major component 121,or a plurality of major components that are shaped to conform over atleast a portion of a wearer, such as human body. The major component 121can be a continuous base portion that is configured to conform over atleast a portion of a wearer. Alternatively, the major component 121includes a plurality of portions, such as a front body panel 121A and aback body panel 121B of the major component 121. The front body panel121A can be coupled to the back body panel 121B at seams 109, 115 usingthe reversible adhesives described herein, alternatively oradditionally, one or more other methods, such as sewing. The majorcomponent 121 is configured to be coupled with minor components, such asa collar 113 or a sleeve 111 via interface 107. In some embodiments, oneor more of the minor components are formed at least partially over atleast a portion of the wearer. In some embodiments, the collar 113 isformed from coupling a first portion of a major component to a secondportion of the major component by folding over the major component alonga fold parallel to an edge of the major component. The major componentis folded to contact the first portion to the second portion via thereversible adhesive described herein. Alternatively or additionally, oneor more other methods are used to couple the first portion to the secondportion of the major component, such as by sewing. In some embodiments,a folded edge 103 is formed from coupling a third portion of a majorcomponent to a fourth portion of the major component by folding over themajor component along the fold edge 103 parallel to an edge of the majorcomponent. The major component is folded to contact the third portion tothe fourth portion via the reversible adhesive described herein.Alternatively or additionally, one or more other methods are used tocouple the third portion to the fourth portion of the major component,such as sewing.

FIG. 2 depicts a portion of a major component 202 coupled to a portionof a minor component 206. The major component 202 and the minorcomponent 206 can be coupled by a reversible adhesive 204. In someembodiments, the reversible adhesive 204 is disposed at least partiallybetween the minor component 206 and the major component 202. In someembodiments, the reversible adhesive is at least partially disposed orembedded within pores of the major component 202 and/or pores of theminor component 206.

The reversible adhesive 204 is capable of maintaining adhesion to themajor component 202 and minor component 206 under conditions in whichthe apparel article is worn, cleaned, and dried, such as about 90° C. orbelow, such as about 70° C. or below, such as about −50° C. to about 60°C., such as about −40° C. to about 50° C., such as about −20° C. toabout 30° C., such as about 0° C. to about 10° C. The composition of thereversible adhesive 204 is configured to release one or both of theminor component 206 and major component 202 when exposed to apredetermined condition. The predetermined condition can be atemperature, such as a temperature above a predetermined temperature, anelectromagnetic energy exposure, a predetermined pH value, orcombinations thereof depending on the composition of the reversibleadhesive 204. The reversible adhesive 204 can be exposed to thepredetermined condition for a predetermined time depending on thecomposition of the reversible adhesive 204. In some embodiments, thecomposition and conditions for assembling and disassembling thereversible adhesive 204 is the same for each minor component 206, or isdifferent for two or more (e.g., each) minor component 206 located on amajor component depending on the composition of the minor component 206.The difference in disassembly conditions is useful for separatingdifferent components sequentially. Separating different componentssequentially enables ease of sorting of various different types ofmaterials that are categorized into different recycle categories. Insome embodiments, the reversible adhesive 204 composition is determinedbased on the composition of the major component 202. The reversibleadhesive 204 composition includes a material that is compatible andcapable of adhering to the composition of the major component 202.

Apparel Product Components

One or more of the apparel product components (e.g., 202, 204) caninclude different forms and compositions, such as animal-derived orplant-based natural fibers and compositions (e.g., cotton, linen, hemp,silk, cashmere, wool, jute, bamboo, leather), regenerated cellulosecompositions (e.g., acetate), synthetic compositions (e.g., fibers,sheets, patches, liners, shells, woven, non-woven), and any materialknown in the apparel product industry. The apparel product componentscan include polymer materials, such as thermoplastic syntheticmaterials. The apparel product components can include one or morematerials including polyester, such as polyethylene terephthalate(referred to herein as “PET”), acrylic, materials generated fromcellulose (e.g., rayon, lyocell, viscose, modal, bamboo), celluloseacetate, polyamide (e.g., nylon), polyether-polyurea copolymer (e.g.,elastane, spandex, Lycra®), polyurethane, neoprene, polyacetal,polypropylene, polyvinyl chloride (PVC), blends thereof, andcombinations thereof. Other materials are also contemplated such apolybutylene terephthalate (referred to herein as “PBT”) andpolybutylene succinate (referred to herein as “PBS”). The apparelproduct components (e.g., 202, 204) can be formed using fibers, such asfinely woven microfibers, filaments, yarns, or combinations thereof.

The apparel products having the apparel product components can bemachine washable, machine dryable, hand washable, dry cleanable, orcombinations thereof. In some embodiments, the apparel products are dryclean only or hand wash only. In some embodiments, the apparel productscan have portions that are sewn together, or the apparel products can befree of sewn portions. Other forms and compositions of apparel productcomponents are also contemplated, such as post-consumer plastic (PCP).In some embodiments, the composition of at least one of the apparelproduct components contains about 25 wt. % or less PCP material, such asabout 1 wt. % to about 20 wt. %, such as about 2 wt. % to about 15 wt.%, such as about 4 wt. % to about 10 wt. %, such as about 6 wt. % toabout 8 wt. %.

At least one of the one or more apparel product components (e.g., 202,204) can be recyclable, such as at least two of the apparel productcomponents. Each of the apparel product components can be the samerecycle category or grade and can be recycled together. Alternatively,at least two of the apparel product components are categorized asdifferent recycle categories or grades and recycled separately.Separating apparel product components from non-recyclable apparelproduct components and/or recyclable apparel products categorized as adifferent grade can be time consuming, expensive, or difficult due tothe manner in which the components are coupled together. It has beendiscovered, that using a reversible adhesive 204 to join componentstogether enables joining the apparel product components, such that theapparel products are wearable and durable for a variety of conditionswithout separation. As used herein, the term “recyclable material”refers to a material that can be processed and used again in newproducts, such as incorporated into new apparel products.

In some embodiments, one or more of the apparel product components haveglass transition temperature (T_(g)) of about −20° C. to about 250° C.,such as about −10° C. to about 200° C., such as 10° C. to about 100° C.In some embodiments, one or more of the apparel product have a meltingtemperature (T_(m)) of about 75° C. to about 200° C., such as 100° C. toabout 175° C., such as about 125° C. to about 150° C.

In some embodiments, the reversible adhesive 204 includes particles 203disposed therein. The particles 203 can be nanoparticles ormicroparticles. The particles 203 can have a diameter of about 1000 μmor less, such as about 20 μm to about 500 μm, such as about 50 μm toabout 400 μm, such as about 100 μm to about 300 μm, such as about 150 μmto about 200 μm. In some embodiments, the particles 203 have a diameterof about 1 μm to about 10 μm, such as about 3 μm to about 5 μm. In someembodiments, the particles 203 have a largest dimension of about 3 nm toabout 100 nm, such as about 5 nm to about 80 nm, such as about 20 nm toabout 60 nm, such as about 30 nm to about 50 nm, or about 100 nm toabout 200 nm, such as about 150 nm to about 175 nm. In some embodiments,the particles 203 are encapsulated in a polymer. In some embodiments,the particles 203 are encapsulated with a polymer that is the same orcompatible (e.g., miscible) with one or more polymers of the reversibleadhesive. The particles can be in the form of plates, fibers, orrod-like particulates distributed through the reversible adhesive. Insome embodiments, the particles are granular, spherical, oblong,rod-shaped, or semi-spherical nanoparticles or macroparticles.

The particles are configured to absorb non-contact electromagneticenergy, such as eddy current induction heating and/or microwave bydirecting the energy to the reversible adhesive, where the particlesabsorb the radiation and convert it to thermal energy. The thermalenergy is sufficient to break the covalent bonds of the reversibleadhesive 204 and release the components 202, 204 from one another.

In some embodiments, the particles can be heated or energized to heat orenergize the reversible adhesive locally to a temperature greater thanthe temperature of the components of the apparel product. In someembodiments, the particles can be heated using electromagnetic energysuch as microwave, ultraviolet, infrared, blue light, or other forms ofelectromagnetic energy. In some embodiments the electromagnetic energycan include one or more of microwave (e.g., wavelength of about 1 mm toabout 1 m), ultraviolet (e.g., wavelength of about 10 nm to about 400nm), infrared (e.g., wavelength of about 750 nm to about 1 mm), visible(e.g., wavelength of about 400 nm to about 750 nm), such as blue light(e.g., wavelength of about 400 nm to about 500 nm), or other forms ofelectromagnetic energy. The particles can be suspended uniformlythroughout reversible adhesive, or the particles can be embedded ordoped into the reversible adhesive, such as a surface of the reversibleadhesive. In some embodiments, the particles are pre-mixed in thereversible adhesive to provide a homogeneous distribution through thereversible adhesive.

The reversible adhesive can be selectively heated by usingmetal-containing particles 203 disposed within the reversible adhesive.The particles can be embedded in the reversible adhesive at aconcentration that enables heat transfer to the adhesive at thetemperature range at which the reversible bonds break. In someembodiments, the apparel product components are maintained intact,without degradation during the heat transfer from an external heatsource to the particles and to the reversible adhesive. In someembodiments, the reversible adhesive includes particles, such asmetal-containing particles, such as an iron containing material, such asiron oxide. In some embodiments, the particles include Fe₃O₄, γ-Fe₂O₃,metallic iron, copper, aluminum, silver, cobalt, nickel, FeN, FePt,FePd, or combinations thereof. In some embodiments, the particlesgenerate heat when exposed to microwave energy, such as from a microwavereactor. In some embodiment, the particles are exposed to microwaveenergy having a frequency of about 915 MHz to about 5 GHz, such as about2.45 GHz to about 4 GHz. In some embodiments, the reversible adhesive204 includes metal-containing particles and the apparel product is freeof any other metallic components such that other portions of the apparelproduct is not selectively heated as the particles are heated.

In some embodiments, the reversible adhesive includes a particle loadingof about 0.01 wt. % to about 20 wt. %, such as about 0.05 wt. % to about5 wt. %, such as about 1 wt. % to about 4 wt. %, such as about 2 wt. %to about 3 wt %, or about 6 wt. % to about 10 wt. %, such as about 7 wt.% to about 9 wt. %, or about 8 wt. % to about 15 wt. %, such as about 10wt. % to about 13 wt. %.

In some embodiments, the particles produce heat when exposed to static(H dc) or alternating (H ac) magnetic fields. The temperature of thereversible adhesive is locally increased by induction from the heatedparticles. In some embodiments, the alternating magnetic field isapplied at a frequency of about 200 kHz to about 1000 kHz, such as about300 kHz to about 900 kHz, such as about 600 kHz to about 800 kHz andstrength of about 2 kA/m to about 30 kA/m, such as about 6 kA/m to about11 kA/m.

In some embodiments, the reversible adhesive is free of metallicparticles, such as for apparel products containing metal components,such as metallic zippers or metallic buttons. In some embodiments, thereversible adhesive is free of metallic particles, such as for apparelproducts composed of material having a glass transition temperatureabove the deactivating temperature. In particular, the reversibleadhesive can be heated to a temperature that breaks the bonds of thereversible adhesive, the temperature being lower than the glasstransition temperature of the apparel product.

Alternatively, or additionally, the particles include shape memorymaterials configured to deform upon exposure to light or heat which isdescribed in further detail relative to shape memory materials describedherein.

Alternatively, or additionally, the particles are configured toilluminate upon activation, such as electrical activation which isdescribed in further detail relative to shape memory materials describedherein.

Assembly of Apparel Product Components

FIG. 3 depicts a process flow diagram of a method 300 for assembling anapparel product according to some embodiments. The method 300 includesapplying 302 a reversible adhesive composition to a portion of a firstcomponent of the apparel product, applying 304 a portion of a secondcomponent of the apparel product to the reversible adhesive, andoptionally curing 306 the reversible adhesive. The reversible adhesivecomposition can be applied 302 using any method known in the industrydepending on the composition of the reversible adhesive composition. Insome embodiments, the reversible adhesive composition is applied by heatgun, printing, spraying, painting, dipping, roll on, screen printing,photolithography, transferring or spreading on by contact, orcombinations thereof. The reversible adhesive composition can be inliquid form or a semiliquid gel form, or a foam when applied. In someembodiments, the reversible adhesive composition includes a foamingagent. The reversible adhesive composition can be crosslinked byapplying a crosslinking condition, such as heat, electromagnetic energy,or combinations thereof. The crosslinking condition can be applied for atime of about 1 second to about 24 hours, such as about 5 seconds toabout 2 hours, such as about 30 minutes to about 1 hour. Once thereaction for crosslinking occurs, the crosslinked reversible compositioncan be cured, such as by reducing the temperature.

Prior to use, the reversible composition can be stored in a kit, such asa two part kit and combined prior to applying to the components.Alternatively, the reversible adhesive composition is stored in a singlecontainer, such as a previously crosslinked reversible adhesive. Thepreviously crosslinked reversible adhesive can be stored as strips orother geometries. In some embodiments, the previously crosslinkedreversible adhesive can be treated by a deactivating condition prior toapplying the adhesive/monomers thereof to the major component or minorcomponent. The previously crosslinked reversible adhesive can bepartially crosslinked or fully crosslinked. The storage container caninclude the reversible adhesive composition that has not yet beencrosslinked. Overtime, the reversible adhesive composition can undergopartial bonding that increases the viscosity and changes dispensingproperties such as flow rate of dispensing and component penetration.The bonding amount depends on time, temperature, and exposure tomoisture. Although the term “applying” is used to describe transferringthe reversible adhesive to the apparel product and pressing thecomponents together, other terms can also be used such as coupling,transferring, contacting, pressing, or combinations thereof.

In some embodiments, such as for reversible adhesive with Diels-Alderbonds, to prevent issues with applying the reversible adhesivecomposition, the reversible adhesive composition, which can have partialbonding with a first viscosity and first molecular weight, can bepre-heated to a temperature of about 100° C. to about 200° C., such asabout 150° C. for about 1 minute to about 30 minutes, such as about 5minutes to about 20 minutes, such as about 10 minutes to about 15minutes. After preheating, at least some of the partial bonds are brokenand the reversible adhesive composition can have a second viscosity andsecond molecular weight. The second viscosity is less than the firstviscosity and the second molecular weight is less than the firstmolecular weight. The viscosity is reduced to a predetermined viscositythat enables dispensing and/or spreading the reversible adhesivecomposition. After the reversible adhesive composition is dispensedbetween components or portions of components, the reversible adhesivecomposition can be allowed to bond by reducing a temperature of thereversible adhesive. For Diels-Alder, a bonding can occur at about 25°C. to about 100° C., such as about 70° C. for about 1 hour to about 7days, such as about 1 hour to about 2 hours.

In some embodiments, components such as monomers are applied to theapparel product in one or more layers and the monomers react with oneanother once applied to the apparel product. In some embodiments, themonomers polymerize (e.g., cure) when applied to the apparel product. Insome embodiments, the monomers do not react or react slowly until curedwith a curing agent, thermal energy, electromagnetic energy, orcombinations thereof. In some embodiments, the reversible adhesive isapplied at a thickness of about 0.02 mm or greater, such as about 0.1 mmto about 5 mm, such as about 0.2 mm to about 3 mm, such about 0.3 mm toabout 0.5 mm, or about 0.6 mm to about 0.8 mm. In some embodiments, thereversible adhesive can have a viscosity of about 1,000 cPs to about10,000 cPs, such as about 3,000 cPs to about 6,000 cPs, such as about3,500 cPs to about 5,000 cPs during application. In some embodiments,the reversible adhesive can be applied in a predetermined pattern on oneor more components of the apparel product using photolithography, suchas by curing by ultraviolet (UV) light.

Curing 306 the reversible adhesive can include any method known in theindustry for curing adhesives, such as air drying, curing by applyingheat, curing by applying electromagnetic energy, such as UV light, orcombinations thereof. In some embodiments, the adhesive is solid uponcuring. Prior to and/or during application, the removable adhesive canbe maintained at a temperature of about 40° C. to about 200° C., such asabout 80° C. to about 100° C. In some embodiments, curing 306 thereversible adhesive further includes applying a force to press thecomponents against one another for a predetermined amount of time. Acure time can range from about 1 second to about 72 hours, such as about1 hour to about 5 hours, such as about 1 minute to about 2 hours, suchas about 10 minutes to about 30 minutes, or about 24 hours to about 48hours. In some embodiments, curing includes exposure to ambientconditions, such as ambient air and humidity.

The method 300 is described in further detail relative to each adhesivecomposition described in further detail herein.

Disassembly of Apparel Product Components

The reversible adhesive can be deactivated during disassembly of theapparel product under a predetermined condition depending on thecomposition of the reversible adhesive. FIG. 4 depicts a process flowdiagram of a method 400 for disassembling an apparel product accordingto some embodiments. The method 400 includes exposing 402 an apparelproduct to a deactivating condition, the apparel product including areversible adhesive between portions of a first and second component ofthe apparel product, separating 404 the first component from the secondcomponent adjoined by the reversible adhesive, and sorting 406 theseparated components. In some embodiments, the reversible adhesive caninclude temperature reversible bonds, such as Diels-Alder bonds,chemical reversible bonds, such as disulfide bonds, thioester bonds,boronate bonds, imine bonds, light reversible bonds, such ascyclodextrin-azobenzene, shape memory materials, benzoxaborole bonds,oxime bonds, acylhydrazone bonds, thiol bonds, mixtures thereof, orcombination(s) thereof. Other reversible bond types are alsocontemplated. In some embodiments, separating 404 further includesremoving threads adjoining one or more components. Additionally, oralternatively, separating 404 further includes removing threadsadjoining one or more portions of one or more components. The threadscan be composed of a recyclable material or a non-recyclable material.In some embodiments, the threads are composed of nylon.

The deactivating condition can be a temperature, such as a temperaturebelow a degrading temperature of the apparel product components andabove a minimum deactivating temperature for deactivating the reversibleadhesive. In some embodiments, the deactivating temperature of thereversible adhesive is about 100° C. to about 180° C., such as about120° C. to about 160° C., such as about 130° C. to about 140° C. In someembodiments, a collection of apparel products are collected and heatedin a process chamber, such as a furnace, a microwave oven, anelectromagnetic oven, an induction oven, or other equipment known in theart configured to transfer heat selectively to the reversible adhesiveswithout significantly heating the apparel material being separated.

The deactivating condition can be a predetermined pH change or apredetermined pH range. In some embodiments, the apparel products areexposed to the deactivating condition in one or more baths, such as oneor more solvent baths having a controlled pH range, such as a basicsolution, a caustic solution, or combinations thereof. Each of the oneor more baths can be configured to mechanically agitate the apparelproducts, such as spinning in a washing machine. The reversible adhesiveis exposed to the one or more baths and reverse the reversible adhesive.In some embodiments, the apparel products can be rinsed after exposureto the deactivating condition to remove monomers and other byproduct(s)of the reversed adhesive.

The deactivating condition can be an exposure to electromagnetic energywithin a predetermined range of wavelengths. In some embodiments, thedeactivating condition is an exposure to one or more of microwave (e.g.,wavelength of about 1 mm to about 1 m), ultraviolet (e.g., wavelength ofabout 10 nm to about 400 nm), infrared (e.g., wavelength of about 750 nmto about 1 mm), visible (e.g., wavelength of about 400 nm to about 750nm), such as blue light (e.g., wavelength of about 400 nm to about 500nm), or other forms of electromagnetic energy. In some embodiments, aportion of the apparel producing including the reversible adhesive canbe stretched to enable penetration of the deactivating condition to thereversible adhesive. In some embodiments, the portion including thereversible adhesive can be composed of a stretchable material, such as amaterial including spandex. Without being bound by theory, it isbelieved that stretching the fabric enables providing tension on theadhesive bonds and increasing an area of exposure to enable penetrationof the electromagnetic energy, such as light to the reversible bonds.

Upon energizing the reversible adhesive, reversible bonds of thereversible adhesive are broken and the viscosity of the reversibleadhesive is substantially reduced. In some embodiments, the reversibleadhesive is soluble in a solution, such as water or in a solvent uponenergizing the reversible adhesive. The broken reversible chemical bondsand reduced viscosity reduces the adhesive strength of the reversibleadhesive. The portions of the components held together by the reversibleadhesive can be separated (e.g., 404) by application of a force, such aspulling the components apart. In some embodiments, separating 404includes separation by gravity or mechanical agitation, such as a tumbledryer, centrifugal separator, or other reactor. In some embodiments,operations 402 and 404 occur substantially simultaneously, such as in atumble dryer with heating applied simultaneously with tumbling or otheragitation. In some embodiments, the components are separated prior tointroducing the separated components into a centrifuge. In someembodiments, the reversible adhesive is separated from the components inthe centrifuge. In some embodiments, the reversible adhesive isdissolved in the centrifuge.

In some embodiments, such as in large scale separation, the apparelproducts can be placed in a process chamber configured to applycentrifugal force on the components of the apparel products to induceseparation of the deactivated adhesives from the apparel components. Thecentrifugal force is configured to pull the depolymerized liquidadhesive (e.g., deactivated reversible adhesive) off the apparelproducts. In some embodiments, the process chamber is a high speedcentrifuge that can be temperature and pressure controlled. In someembodiments, the apparel products can be processed in the device at arotational speed of about 50 rpm or greater, such as about 100 rpm toabout 150,000 rpm, such as about 500 rpm to about 1,000 rpm, such asabout 1,500 to about 3,000 rpm, or about 4,000 rpm to about 5,000 rpm.The apparel products can be processed in the process chamber for about10 seconds to about 48 hours, such as about 20 seconds to about 24hours, such as about 30 seconds to about 16 hours, such as about 5minutes to about 20 minutes, or about 30 minutes to about 1 hour, orabout 2 hours to about 4 hours, or about 6 hours to about 8 hours. Insome embodiments, the deactivated reversible adhesive can be spun out ofa chamber volume of the process chamber. In some embodiments, each ofthe one or more components of the apparel products can be grouped withinthe process volume by product density or size. In some embodiments, theseparated components are sorted by passing the components through one ormore sieves. Small components such as buttons can pass through openingsin the sieve and be separated from the bulk components. The one or morecomponents can also be sorted by separating out buoyant components thatfloat to the surface of a solution and/or non-buoyant components thatsink to the bottom of a solution. In some embodiments, the componentsare disposed at different heights within a solution based on a densityof the components. For example a density of a nylon can be about 1.0g/cc, a density of polyester can be about 1.3 g/cc and a density ofcotton can be 1.5 g/cc. Each of the nylon, polyester, and cotton can beseparated from one another based on differences in density. In someembodiments, different components are sorted by differences in colorusing computer vision methods.

Sorting 406 the separate components can include categorizing thecomponents by recycle groups to be recycled, reused, or discarded inaccordance with the recycle group or category. In some embodiments, thereversible adhesive material can be collected, recycled, reused,discarded, or combinations thereof. In some embodiments, the componentsare separated based on material density, color, rheology, or otherphysical attribute. Once grouped, each of the components can be furtherrinsed or washed with a solvent, surfactant, or other solution to removedebris or residual reversible adhesive. Each group of components can befurther characterized, such as by spectroscopy, chromatography (e.g.,gel permeation chromatography), or other test method. The testing candetermine the quality of the components and method for recycling thematerials. Recycling can be done in any method known in the industry,such as by shredding, granulating, melting, extruding, pelletizing, orcombinations thereof. After sorting the components by a first attribute,such as density, the components can be further separated based onadditional attributes such as a second attribute, such as color.

Apparel products assembled with reversible adhesives described hereinare disassembled by treating the reversible adhesive with a deactivatingcondition. The deactivating condition converts the reversible adhesiveto a treated reversible adhesive with a reduced viscosity and/or reducedadhesive properties. The components coupled together by the reversibleadhesives can be separated once the reversible adhesive is treated. Thetreated reversible adhesives can be removed from the components by aforce, such as a centrifugal force in a spinner. Components of theapparel product can be sorted and separated by a physical attribute,such as by component density, which can be detected by difference incomponent buoyancy when suspended in a fluid. In addition to usingbuoyancy force to separate componnets of different densities, othermethods are also contemplated such as near-infrared optical methods todifferentiate components by component chemistry. The separatedcomponents can be further sorted by a second physical attribute such ascolor (e.g., pigment intensity).

In some embodiments, a large number of apparel products are massprocessed. The apparel product components are first spread apart onto asurface, such as a conveyor belt. Arranging the apparel productcomponents can include running a conveyor belt at a speed below acontainer of numerous apparel components. At the bottom of thecontainer, a dispenser opens and closes at a frequency to drop a smallnumber of apparel product components onto the conveyor belt. The speedof the conveyor belt, the size of the opening of the dispenser at thebottom of the container, and a cycle time of the dispenser opening andclosing are tuned to control the amount of the components in each groupand how far apart the components are distributed along the conveyorbelt. When the apparel product components travel on the conveyor beltsin small groups, mechanical grippers with long and slender tips are usedto pinch and pick up individual components. The grippers can be guidedby a computer vision algorithm with the ability to detect an attributesuch as color.

Reversible Adhesive Backbone

As used herein, the term “backbone” refers to a polymer structure thatcan be further functionalized with functional groups to form the bondsdescribed in more detail herein, such as Diels-Alder bonds, disulfidebonds, thioester bonds, boronic acid bonds, imine bonds,cyclodextrin-azobenzene bonds, shape memory materials, or combinationsthereof. The reversible adhesive backbone can include one or moremonomers (as reacted monomeric units) that have been polymerized orcopolymerized. In some embodiments, the reversible adhesive includesmonomeric units of acrylate, methacrylate, acrylic, ethylene, propylene,styrene, vinyl acetate, vinyl ester monomers, or combinations thereof.

The reversible adhesive can include acrylic monomeric units, such asacrylic acid (AA), methacrylic acid (MAA), esters of AA and MAA,itaconic acid (IA), crotonic acid (CA), acrylamide (AM), methacrylamide(MAM), and derivatives of AM and MAM, e.g., alkyl (meth)acrylamides.Esters of AA and MAA include alkyl, hydroxyalkyl, phosphoalkyl andsulfoalkyl esters, e.g., methyl methacrylate (MMA), ethyl methacrylate(EMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA),hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA),hydroxybutyl acrylate (HBA), methyl acrylate (MA), ethyl acrylate (EA),butyl acrylate (BA), 2-ethylhexyl acrylate (EHA), cyclohexylmethacrylate (CHMA), benzyl acrylate (BzA), isooctyl acrylate, laurylacrylate, stearyl acrylate, and phosphoalkyl methacrylates (e.g., PEM).In some embodiments, the backbone polymer can further include gelcompositions, such as polyethylene glycols (PEG), poly(2-oxazoline),poly(2-oxazine), derivatives thereof, and mixtures thereof.

In addition to the backbone polymer, any of the reversible adhesivesdescribed herein can further include additional additives or polymers,such as tackifiers, antioxidants, nucleators, energy absorbers, curingagents, or combinations thereof. In some embodiments, these additionaladditives or polymers can be present in the reversible adhesive in anamount of about 1 wt. % to about 40 wt. %, such as about 5 wt. % toabout 30 wt. %, such as about 10 wt. % to about 20 wt. %.

The reversible adhesives have adhesive properties suitable to withstandnormal use, cleaning, and drying of the apparel products. In someembodiments, the reversible adhesive can have a T-peel strength of about5 N/cm-width to about 100 N/cm-width, such as about 10 N/cm-width toabout 50 N/cm-width, such as about 20 N/cm-width to about 30 N/cm-width,as tested according to ASTM D1876 (2015). As used herein, adhesivestrength, such as T-peel can be measured using any test methods known inthe industry. Moreover, adhesive strength can depend on the adhesive,the mechanical strength of the component, the mechanical strength of theadjoined structure, the type of adjoined structure, or combinationsthereof. The adjoined structure can be a butterfly joint or an overlapjoint.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In some embodiments, the reversible adhesive includes multiple layerssuch as a primer layer disposed between the component of the apparelproduct and an adhesive layer that includes the reversible bonds.

The reversible adhesives described herein are different fromconventional adhesives, such as adhesives that melt with no bonds beingbroken. Without being bound by theory, the crosslinking covalent bondsdescribed herein provide adhesive strength and an ability to bond to thematerials of the apparel product components. It is believed that whendisassembly conditions are met, these bonds will break and cause thereversible adhesive to lose strength and tackiness. The breaking of thebonds enable complete separation between the adhesive and the apparelmaterial in a chemical process. Additionally, the molecular weight ofthe reversible adhesive before breaking the bonds (e.g., can be up toinfinite molecular weight) is higher than the molecular weight of thereversible adhesive after breaking the bonds.

In contrast, conventional thermoplastic adhesives do not containcrosslinking bonds. When heated, conventional adhesives become softerand easier to flow because of increased chain mobility and little or nocovalent bonds are broken. The molecular weight of the conventionaladhesive remains substantially the same before and after heating theadhesive, which would otherwise make any disassembly very difficult. Theheated conventional adhesive remains viscous and tacky due to the highmolecular weight. As a result, the two substrates being bonded by theconventional adhesive may be separated but it is difficult to separatethe adhesive from the substrates. The melting of thermoplastic adhesivesis a physical process rather than a chemical process described relativeto the reversible adhesives described herein.

Cycloalkene Bonding

In some embodiments, the reversible adhesive includes thermoreversiblebonds, such as cycloalkene bonds, such as cyclo-monoalkene bond. Thecycloalkene bonds can be part of a polymer network such as any of thebackbone polymers described herein. In some embodiments, the polymernetwork includes a polyester, polypropylene, polyethylene, poly(esterurethane), copolymers thereof, or combinations thereof. The cycloalkenebonds, also referred to herein as “Diels-Alder” bonds can be formedbetween various diene and dienophile groups, such as maleimide and furangroups, such as bismaleimide and trifunctional furan. The diene anddienophile composition can be selected such that a temperature used toreverse the reversible adhesive can be controlled to be within apredetermined temperature, such as below the temperature at which thecomponents degrade and above a temperature the apparel product can beworn, used, cleaned, and dried. The diene and dienophile group ratioscan be selected to obtain reversible adhesive having differentproperties, such as cross-linking densities. In some embodiments, thereversible adhesive is doped with Diels-Alder functional groups. In someembodiments, the copolymer functionalized with diene includes furfurylmethacrylate. In some embodiments, the diene copolymer, such as furfurylmethacrylate is present in the reversible adhesive in an amount 10 wt. %to 99 wt. %, such as about 20 wt. % to about 80 wt. %, such as about 20wt. % to about 30 wt. %, based on the weight of the reversible adhesive.

In some embodiments, adducts form between the diene and dienophilegroups at a temperature of about 80° C. or lower, such as about 20° C.to about 80° C., such as about 30° C. to about 70° C. In someembodiments, the adducts are formed after about 1 minute to about 2hours at the temperature, such as about 5 minutes to about 1 hour, suchas about 10 minutes to about 30 minutes. The reversible adhesiveincluding the adducts include cross-linked bonds having bond strengthsand bonds with suitable adhesion properties for apparel products. Theadducts can be debonded (reversible bond) at temperatures of about 80°C. or greater, such as about 90° C. to about 200° C., such as about 100°C. to about 120° C., such as about 140° C. to about 160° C. Thecross-linked bonds of the molecular structure of the reversible adhesivecan break, resulting in lower molecular weight and low modulus as wellas reduced viscosity and increased solubility in a solvent. As usedherein, a “solvent” refers to an organic solvent such as an aliphaticsolvent, aromatic solvent, an alcohol solvent, a glycol ether solvent,or combinations thereof. In some embodiments, a solvent is selecteddepending on the polymer backbone used for a polymer of the adhesive. Aforce, such as a centrifugal force of a device can separate componentsthat are joined together by the reversible adhesive and the reversibleadhesive from the components once the reversible adhesive bond isbroken. In some embodiments, the apparel product can be heated whilebeing rotated in a centrifuge at a temperature that can break theDiels-Alder bonds.

The reversible adhesive can be prepared by forming a polyketone. Thepolyketone can include carbon monoxide, propylene, ethylene, or acombination thereof. In some embodiments, the propylene to ethyleneweight ratio is about 1:0 to about 10:1, such as about 1:1 to about 5:1,such as about 2:1 to about 4:1. The polyketone can be grafted withfurfurylamine. The grafted polyketone can be at least partiallyfunctionalized with furan groups and crosslinked with bismaleimide.

Bismaleimide resins can include, but are not limited to,bis(3-ethyl-5-methyl-4-maleimidophenyl)methane,4,4′-bismaleimido-diphenylmethane, 1,4-bismaleimido-2-methylbenzene andmixtures thereof; modified and partially advanced modified bismaleimideresins containing Diels-Alder comonomers; and a partially advancedbismaleimide based on 4,4′-bismaleimido-diphenylmethane and allylphenylcompounds or aromatic amines. In some embodiments, the bismaleimidesuseful for the reversible adhesives described herein include abismalemide having about 2 to about 100 carbons, such as long-chainedbranched 36-carbon bismaleimide.

Suitable Diels-Alder dienophiles include styrene and styrenederivatives, bis(propenylphenoxy) compounds,4,4′-bis(propenylphenoxy)sulfones,4,4′-bis(propenylphenoxy)benzophenones, 4,4′441-methyl ethylidene),bis(2-(2-propenyl)phenol),Bis(3-ethyl-5-methyl-4maleimidophenyl)methane, 1,4-Di(maleimido) butane,N,N′-(1,3-Phenylene)dimaleimide, N,N′-(1,4-Phenylene)dimaleimide,N,N′-(o-Phenylene)dimaleimide, and1,1′-(Methylenedi-4,1-phenylene)bismaleimide.

Bismaleimides (dienophiles) can be based on4,4′-bismaleimido-diphenylmethane and an allylphenyl compound, such asdiallylbisphenol-A. Other bismaleimides can include a nucleophilicaddition of a nucleophile (or a carbanion) to an α,-unsaturated carbonylcompound including copolymers of bismaleimide and aromatic diamines,such as 4,4′-bismaleimido-diphenylmethane/4,4′-diaminodiphenylmethane.In some embodiments, bismaleimide resins are based on4,4′-bismaleimido-diphenylmethane. Alternative crosslinking agents(dienophiles) may include acetylenes and thioesters substituted with anelectron-withdrawing group.

The amount of bismaleimide can be controlled to achieve a predeterminedcrosslinking density. In some embodiments, the diene group to dienophilemolar ratio, such as furan group to maleimide molar ratio, is about 5:1to about 1:1, such as about 4:1 to about 2:1, such as about 3:1. In someembodiments, the furfuryl moiety to bismaleimide molar ratio is about2:1 to about 1:2, such as about 1:1 to about 2:3.

Without being bound by theory, it is believed that reversible adhesivesincluding higher dienophile to diene molar ratios are considered to havelower network mobility and require higher temperatures for crosslinkbonds to break. Depending on the apparel product materialconsiderations, a temperature range at which Diels-Alder bonds break isselected and tuned by controlling a molar ratio of dienophile to diene.Controlling a temperature range at which the reverse reaction occursenables preventing premature degradation of apparel products duringnormal use, cleaning, and overall life of apparel products.

Additionally, it is further believed that the temperature range at whichthe reverse reaction occurs can be controlled by adjusting relativeamounts of monomers that make up the polymer backbone of the adhesive.In some embodiments, increasing an ethylene content, such as to anamount of about 20 wt. % to about 50 wt. % ethylene of total weight ofethylene and propylene used for the polymerization reaction, canincrease a temperature range at which the reverse reaction occursrelative to propylene backbone adhesives that do not include ethylene.Lower network mobility can also lead to longer times to break the bonds.Thus, monomer content and dienophile to diene molar ratio can becontrolled to enable a suitable time to disassemble the apparelproducts, such as about 10 seconds to about 5 hours, such as about 30seconds to about 1 hour, such as about 1 minute to about 30 minutes.

The reversible adhesive can be heated to the temperature range at whichthe reversible bonds break, while maintaining a temperature of thesurrounding materials to prevent degradation of the other components ofthe apparel products or the debonding of another reversible adhesivedesigned to be debonded at a different condition to further separateadditional components sequentially. The reversible adhesives areparticularly advantageous with the particles 203 described relative toFIG. 2 .

In some embodiments, the reversible adhesive includes a monomerincluding a diene, such as a diene acrylate or methacrylate and adienophile, such as a bismaleimide crosslinking agent.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive with Diels-Alder bonds havea bond strength of about 4 mPa to about 12 mPa, such as about 5 mPa toabout 10 mPa, such as about 5 mPa to about 8 mPa at 23° C. when bondedto a major and/or minor component described herein. In some embodiments,the reversible adhesive with Diels-Alder bonds have a bond strength ofabout 0.25 mPa to about 4 mPa, such as about 0.5 mPa to about 3 mPa,such as about 1 mPa to about 2 mPa at 80° C. when bonded to a majorand/or minor component described herein.

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C. Asused herein, unless otherwise indicated, the term “modulus” refers totensile modulus which is measured using a method based on ASTM D412 formaterials having a modulus between 3 MPa to about 100 MPa or based onASTM D638 for materials having a modulus from about 100M Pa to 3500 MPa.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In some embodiments, the reversible adhesive includes about 70 wt. % toabout 85 wt. % 2-ethylhexyl acrylate (EHA), about 3 wt. % to about 15wt. % ethyl acrylate (EA), about 2 wt. % to about 10 wt. % methylmethacrylate (MMA), about 0 wt. % to about 7 wt. % furfuryl methacrylate(FFMA), about 1 wt. % to about 7 wt. % acrylic acid (AA), and about 0.1wt. % to about 1 wt. % n-dodecyl mercaptan (n-DDM).

Thioester Bonding

In some embodiments, the reversible adhesive includes pH reversibleadhesives, such as reversible bonds produced by reversible covalentlinkages, such as a linkage formed between an electrophilic moiety and anucleophilic moiety. In some embodiments, reversible covalent linkages,such as thioester linkages can be formed from reacting an electrophilicmoiety or electrophilic compound and a nucleophilic moiety ornucleophilic compound, such as thiol. The electrophilic moiety orelectrophilic compound can include an acrylamide, alkyl halide, alkylsulfonate, aziridine, epoxide, haloacetamide, maleimide, sulfonateester, acid halide, carboxylic acid, acrylate, methacrylate,pentafluorophenyl groups, or combinations thereof. The electrophilicmoiety containing materials can be selected based on the backbonematerial and the predetermined conditions (e.g. pH range) for reversingthe reversible adhesive.

Thioester linkages can be formed as part of thioester exchangereactions, such as thiol-thioester exchanges. A thiol-thioester exchangeincludes a thiolate anion reaction with a thioester to form thiolate andthioester products. Thioesters can also hydrolyze in water to formcarboxylic acids. The relative rates of exchange and hydrolysis arecompeting reactions that can be controlled by exposing the reactants toa solution with a predetermined pH to aid the desired reaction such as areaction that favors or limits hydrolysis over thiol-thioester exchange.Hydrolysis is typically considered an unstable state. In someembodiments, the reversible adhesive includes one or more of thematerials such as polymers described relative to thermoreversibleadhesives. The reversible adhesive contains a reaction product ofthiol-thioester reactants.

The reversible adhesive can be formed and is stable when exposed tosolutions with a pH of about 3 to about 8, such as about a pH of about 4to about 7, such as about 5 to about 6. In some embodiments, thereversible thiol-thioester exchange reaction can occur at ambientconditions. In some embodiments, the reversible adhesives are cured byexposure to UV radiation. In some embodiments, the reversible adhesivescan be reversed by exposure to UV radiation.

The reversible adhesive can be formed by combining a first crosslinkablepolymer having thiol moieties and a second crosslinkable polymer havingelectrophilic crosslinkable moieties. The crosslinkable moieties of thesecond crosslinkable polymer are capable of reacting with the thiolmoieties of the first crosslinkable polymer to form thioester linkagesbetween the first and second crosslinkable polymers. The firstcrosslinkable polymer can further include additional moieties such asthioester, alcohol, amine, and combinations thereof. In someembodiments, a reversible adhesive copolymer that contains an adhesivecomponent such as butyl acrylate and a crosslinkable component such aspoly(thiophenyl methacrylate) can be reacted with a bisthiol (i.e. 1,4dithiobutane) or a bisamine (cysteamine dihydrochloride) to providecrosslinking. For crosslinking with a bisthiol, reversing thecrosslinking would be based on the hydrolysis of thioesters. Forcrosslinking with a cysteamine the disulfide bond is the reversiblebond.

The reversible adhesive can be formed by combining a first crosslinkablepolymer having thioester moieties and a second crosslinkable polymerhaving crosslinkable moieties. The crosslinkable moieties of the secondcrosslinkable polymer are capable of reacting with the thioestermoieties of the first crosslinkable polymer to form thioester linkagesbetween the first and second crosslinkable polymers. The firstcrosslinkable polymer can further include additional moieties such asthiol, alcohol, amine, and combinations thereof. As used herein, a“thioester” is a compound having the formula R—S—CO—R′, where R and R′are, independently carbon and/or hydrogen containing groups having 1 toabout 29 carbons, such as about 2 to about 20 carbons, such as about 5to about 10 carbon atoms. As used herein, a “thiol” is a compound havingthe formula R—SH, where R is a carbon and/or hydrogen containing group.As used herein a “unit” is a monomeric unit that is part of a polymer ofthe present disclosure.

Table I lists several non-limiting examples of thioesters and thiolsthat can be used to form the reversible adhesives described herein.

TABLE 1 Example Thiols and Thioesters Thioesters Thiols

Acylated thiophenol thiophenol

Acylated 2-mercaptopyridine 2-mercaptopyridine n-oct-SAc n-oct-SHAcylated 1-octanethiol 1-octanethiol

Acylated methyl 3-mercaptopropionate methyl 3-mercaptopropionate

Acylated 2- 2-(boc-amino)ethanethiol (boc-amino)ethanethiol Boc =tert-butyloxycarbonyl Boc = tert-butyloxycarbonyl

The reversible adhesive can include a first crosslinkable polymer havingactivated esters (e.g., N-hydroxysuccinimide) and a second crosslinkablepolymer having thiol moieties functionalized to the backbone or formedas part of the backbone.

In some embodiments, the reversible adhesive is reversed by exposing thereversible adhesive to a solution. The solution can have a pH below 3 orabove 8. In some embodiments, the reversible adhesive degrades and thecomponents held together by the reversible adhesive can be separated atpH levels below 3, such as about 1 to about 2.9, such as about 1.4 toabout 2.8, such as about 1.6 to about 2.6, In some embodiments, at pHlevels above 8 pH, such as about 8.1 to about 14, such as about 9 toabout 13, such as about 10 to about 12, the reversible adhesive degradesand the components held together by the reversible adhesive can beseparated. The degradation of the reversible adhesive includeshydrolyzing the thiol-thioester. The material of the apparel productcomponents are maintained without degradation. In some embodiments,thioesters having a pK_(a) of about 2 to about 8 pK_(a) reacts withthiols with a pK_(a) of about 2 to about 10 pK_(a). In some embodiments,the solution can include solvents, such as dimethylformamide,dimethylsulfoxide, acetone, ethyl acetate, toluene, or chloroform. ThepH of the solution can be adjusted using a nucleophilic catalyst, suchas an amine catalyst, such as dimethylaminopyridine,1,4-diazabicyclo[2.2.2]octane, quinuclidine.

In some embodiments, the solution includes a thiolate compound. Thethiolate compound can include a linear, branched and/or dendriticmulti-thiol macromolecule, poly(ethylene glycol) thiol, thiol containingglycerol, thiol containing peptide, cysteine, cystine, alkyl ester ofcysteine, alkyl ester of cystine, MeSCH₂SH,(R)/(S)-3-methyl-3-sulfanylhexan-1-ol, ethanethiol, 1-propanethiol,2-propanethiol, butanethiol, tert-butyl mercaptan, pentanethiols,thiophenol, dimercaptosuccinic acid, thioacetic acid,5-mercapto-4H-[1,2,4]triazol-3-ol, 2-mercaptoacetamide,2-mercaptoethanol, 1,2-ethanedithiol, ammonium thioglycolate,cysteamine, methyl thioglycolate, thiolactic acid,1-mercapto-2-propanol, 2-methoxyethanethiol, 3-mercapto-1-propanol,2,3-dimercapto-1-propanol, 1-thioglycerol, mercaptosuccinic acid,4-ethyl-5-mercapto-4H-1,2,4-triazol-3-ol, N-carbamoyl-L-cysteine,2-methyl-3-sulfanylpropanoic acid, 4-mercaptobutyric acid,N-acetylcysteamine, 3-methyl-1-butanethiol, 1,5-pentanedithiol,4-chlorothiophenol, 4-aminothiophenol, benzyl mercaptan,2-furanmethanethiol, 3-mercaptohexanol, furfuryl thiol, derivativesthereof, a disulfide complex of one or more thereof, and anycombinations thereof.

Without being bound by theory, it is believed that the thio-thioesterexchange reaction between the thioester linkages in the reversibleadhesive and the thios of the thiolate compound leads to dissolution ofthe reversible adhesive.

In some embodiments, a plurality of apparel products that include thereversible adhesive can be soaked in the solution and agitated. In someembodiments, the plurality of apparel products can be soaked in a firstsolution having a first pH, then soaked in a second solution having asecond pH. In some embodiments, the first pH can be less than 3 pH andthe second pH can be greater than 8 pH. In some embodiments, the firstpH can be greater than 8 pH and the second pH can be less than 3 pH. Insome embodiments, the apparel product can be rinsed after the first soakand/or rinsed after the second soak. The reversible adhesive formationand reversal can occur at ambient conditions, such as a temperature ofabout 16° C. to about 35° C., such as about 18° C. to about 26° C.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In some embodiments, the reversible adhesive includes a copolymer ofpoly(thiomethacrylate)-r-(oligo(ethylene glycol)methacrylate). Theoligo(ethylene glycol)methacrylate (OEGMA) component provides a watersoluble component and the thiomethacrylate component can provide thecrosslinkable group. In some embodiments, the reversible adhesive is areaction product of a thioester having the formula below. The thioestercan be bonded to any of the thiols described herein.

R¹ is a hydrogen, a linear hydrocarbon, a cyclic hydrocarbon, or abranched hydrocarbon, such as an alkyl or aromatic group. R² is acarboxyl group or a carbonyl group substituted with a linearhydrocarbon, a cyclic hydrocarbon, a branched hydrocarbon, or an ethergroup. In some embodiments, R² promotes solubility of the polymer in asolvent, such as an organic solvent, or in an inorganic solvent, such aswater. In some embodiments, R² is a methacrylate or acrylate. R³ and R⁴are each independently hydrogen, a linear hydrocarbon, a cyclichydrocarbon, or a branched hydrocarbon, such as a methyl or ethyl group.X and W are each independently hydrogen, a linear hydrocarbon, a cyclichydrocarbon, or a branched hydrocarbon, such as an alkyl or aromaticgroup. Each of “n” and “m” are independently a number from 1 to 1000,such as 100 to 800.

In some embodiments, the reversible adhesive is a reaction product of athioester having the formula below.

R¹ is a hydrogen, a linear hydrocarbon, a cyclic hydrocarbon, or abranched hydrocarbon, such as an alkyl or aromatic group. R₃, R₄, and R₅are each independently a hydrogen, a linear hydrocarbon, a cyclichydrocarbon, or a branched hydrocarbon, such as a methyl or ethyl group.X and W are each independently a hydrogen, a linear hydrocarbon, acyclic hydrocarbon, or a branched hydrocarbon, such as an alkyl oraromatic group. Each of “n,” “m,” and “y” are independently a numberfrom 0 to 1000, such as 100 to 800.Disulfide Bonding

In some embodiments, the reversible adhesive includes pH reversibleadhesives, such as reversible bonds produced by disulfide bonds. In someembodiments, the disulfide bonds are formed using any of the reversibleadhesive backbone materials described herein, such as acrylic,methacrylic, derivatives thereof, or combinations thereof. In someembodiments, the reversible adhesive is a reaction product of a monomerincluding a sulfhydryl (thiol) group and oxidizing agents, such asiodine and oxygen-containing materials, such as sodium periodate, air,diatomic oxygen, 3,3′-dithiopropionic acid, gluthathione disulphide, orcombinations thereof. The thiol groups can be any of the thiol groupsdescribed above with respect to thiols and can be converted to disulfidebonds by oxidizing the monomer. In some embodiments, the monomerincluding the thiol group is a reaction product of an amine containingmonomer and 2-iminothiolate. In some embodiments, forming the disulfidebond is catalyzed with a disulfide derivative, such as pyridyl disulfideor 5-thio-2-nitrobenzoic acid.

In some embodiments, the reversible adhesive is formed byco-polymerization of N,N′-bis-acryloylcystamine with acrylamide in waterto obtain disulfide-containing poly(acrylamide). Thedisulfide-containing poly(acrylamide) is formed by oxidation using a lowmolecular weight disulfide such as cysteamine, 2-hydroxyethyl disulfide,3,3′-dithiodipropionic acid, or glutathione disulfide. In someembodiments, the reversible bond is reversed using dithiothreitol,glutathione, 1-cysteine, or combinations thereof. In some embodiments,the disulfide-containing poly(acrylamide) is incorporated into otherpolymer networks including the backbone polymers described herein.

The reversible adhesive can be formed at a pH range of about 5 pH toabout 11 pH, such as about 6 to about 10, such as about 7 to 9. In someembodiments, the reversible adhesive bonds can include additionalpolymers including other pH sensitive bonds, such as thiol groups orother pH sensitive groups described herein. Other pH sensitive bondsthat can be included in polymers of the reversible adhesive includeketals that are labile in acidic environments, acetals, imines oriminiums, silicon-oxygen-carbon linkages, silicon-nitrogen linkages,such as silazanes, silicon-carbon linkages, such as arylsilane,vinylsilanes, and allylsilanes, bonds formed from maleic anhydridederivatives and amines, ortho esters, hydrazones, activated carboxylicacid derivatives, and combinations thereof.

Without being bound by theory, it is believed that a rate of oxidationof thiol, such as in air, can depend on pH. The oxidation can proceedgenerally in the following general mechanism.R—SH+H₂O⇄R—S⁻+H₃O⁺R—S⁻+O₂⇄R—S′+O₂ ⁻2R—S′R—S—S—R

R is an atom or molecule containing carbon, hydrogen, or combinationsthereof. In some embodiments, the rate of disulfide formation can beincreased by increasing a concentration of free radicals, such as byintroducing the reactants to ammonium persulfate andtetramethylethyldiamine.

In some embodiments, the reversible adhesive includes adisulfide-containing polyester. In some embodiments, the reversibleadhesive can be cured by exposure to UV radiation. In some embodiments,the molecular weight distribution of the reversible adhesive isbroadened by increasing a time of exposure to the UV radiation.

The reversible adhesive can be reversed by altering the pH outside ofthe formation range. Without being bound by theory, it is believed thata change in pH alters a solubility of the polymer having the disulfidebonds. In some embodiments, the apparel products having the reversiblebonds can be submerged in a solution having a pH outside of the pH rangeat which the reversible adhesive is formed, such as about 1 pH to about6 pH, such as about 2 pH to about 5 pH, such as about 3 pH to about 4pH. The reversible adhesive can be reversed at pH below 6 or a pH above7, such as a pH of about 1 to 2, or about 2 to about 3, or about 3 toabout 4, or about 7 to about 8, or about 8 to 9, or about 9 to 10, orabout 11 to 12, or about 12 to about 13, or about 13 to about 14. The pHof the solution can be tuned, altered, or buffered by adding one or moreof carboxylic acids, imidazole, pyridine, phenols, polyamines, orcombinations thereof. The reversible adhesive formation and reversal canoccur at ambient conditions, such as a temperature of about 16° C. toabout 35° C., such as about 18° C. to about 26° C. In some embodiments,the apparel product is submerged for about 1 second to about 24 hours,such as about 10 seconds to about 10 minutes, such as about 30 secondsto about 50 minutes, or about 20 minutes to about 3 hours.

Alternatively, or additionally, the reversible adhesive having disulfidebonds can be reversed by using reducing agents such as glutathione,1-cysteine, or combinations thereof. Alternatively, or additionally, thereversible adhesive having disulfide bonds can be reversed using any ofthe thiols described herein. In some embodiments, the reversibleadhesive having disulfide bonds can be reversed using monothiols,dithiols, phosphines, and combinations thereof.

In some embodiments, disulfide moieties include cystamine, cystin,N,N′-bisacryloyl-cystamine, or combinations thereof. In someembodiments, disulfide moieties can be introduced into a polymericnetwork simultaneously with radical polymerization.

In some embodiments, the reversible adhesive includes gels such aspoly(ethylene glycol-block-propylene glycol-block-ethylene glycol)copolymers. In some embodiments, the reversible adhesive includescompositions having a structure:

R¹ and R² are each independently hydrogen, linear hydrocarbon, branchedhydrocarbon, or cyclic hydrocarbon. In some embodiments, R¹ and R² areeach a polymer having the same type of monomeric units. In someembodiments, R¹ and R² are each a polymer having the different type ofmonomeric units. Each of the polymers are selected based on solubilityin a predetermined solvent or other physical properties.

Without being bound by theory, it is believed that the disulfide groupcan be inserted to any polymer backbone structure between crosslinkingbonds. In some embodiments, at least one of the cross-linked polymersbeing crosslinked is soluble in a solvent.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

Boronate Bonding

In some embodiments, the reversible adhesive includes reversiblecovalent bonds produced by reversible Lewis acid and Lewis baseinteractions. In some embodiments the Lewis acid can include monomerswith boronic acid moieties, such as a phenylboronic acid. The Lewis acidcan be crosslinked with monomers having other moieties (e.g., Lewisbase). The other moieties can include diols. In some embodiments, theother moieties include amine, catechol, silanol, fructose, glucose,galactose, sorbitol, and combinations thereof. In some embodiments, thecovalent bonds are formed between boron and oxygen, such as boronateester bonds, such as cyclic boronic esters (e.g., 5, 6, or 7 memberrings). In some embodiments, the covalent bonds are formed between boronand nitrogen.

In some embodiments, the monomers include two or more boronic acidmoieties. The boronic acid moieties are attached to aromatic rings. Thearomatic rings to which the boronic acid moieties are attached may besubstituted with additional functional groups. In some embodiments, oneor more aromatic rings are substituted with an electron withdrawinggroup, such as a nitro group (—NO₂). The two or more boronic acidmoieties may be attached to the same aromatic ring, as for example, in1,3-benzenediboronic acid (BDBA), or the boronic acid moieties may beattached to different aromatic rings on the same cross-linker molecule.In embodiments where the boronic acid moieties are attached to differentaromatic rings, the aromatic rings may be separated by a linker. Thelinker may include a polymer core, such as any of the polymer backbonesdescribed herein useful for forming adhesives, such as acrylate. In suchembodiments, the polymer core of the linker preferably includes about 1to about 100 monomer units, such as about 10 to about 50 monomer units,such as about 20 to 30 monomer units. The polymer backbone can beattached to the boronic acid-containing aromatic rings through an amidelinkage.

It has been discovered that the moieties can be selected and combined tocontrol a degradation of the reversible adhesive at a predetermined pHrange. In some embodiments, the boronic acid ester bond can be formed ata pH of about 7 pH to about 14 pH, such as about 7.4 pH to about 10 pH,such as about 8 pH to about 9 pH, or about 11 pH to about 12 pH. Theboronic acid ester bond can be reversed at a pH of below 7 pH, such asabout 1 pH to about 6 pH, such as about 2 pH to about 5 pH, such asabout 3 pH to about 4 pH. The reversible adhesive formation and reversalcan occur at ambient conditions, such as a temperature of about 16° C.to about 35° C., such as about 18° C. to about 26° C.

The apparel product can be submerged in a solution having a reduced pH.The pH of the solution can be adjusted by adding an acidic compound suchas mannitol, such as about 80 mM to about 200 mM mannitol. In someembodiments, a pH of the solution can be controlled using any processknown in the industry such as addition of HCl and/or KOH.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In some embodiments, the reversible adhesive includes a copolymer thatis a reaction product of boronic acid groups and a crosslinkinggroup(s). In some embodiments, the crosslinking group is a disaccharideor an oligosaccharide. In some embodiments, the reversible adhesive is areaction product of a compound having a boronic acid group having thestructure shown below.

R¹ and R² are each independently hydrogen, a linear hydrocarbon, acyclic hydrocarbon, or a branched hydrocarbon, such as a methyl or ethylgroup. R³ is a carboxyl group or a carbonyl group substituted with alinear hydrocarbon, a cyclic hydrocarbon, a branched hydrocarbon, or anether group. In some embodiments, R³ is a methacrylate or acrylate. Xand W are each independently a hydrogen, a linear hydrocarbon, a cyclichydrocarbon, or a branched hydrocarbon, such as an alkyl or aromaticgroup. Each of n and m are independently integers between 1 and 1000. Insome embodiments, the phenyl group shown in the formula is substitutedwith a nitrogen containing group, an oxygen containing group, orcombinations thereof. In some embodiments, R₁, R₂ and/or R₃ can include(meth)acrylate groups to adjust solubility, thermal properties, orcombinations thereof.

In some embodiments, the reversible adhesive is a reaction product of acompound having a boronic acid group having one or more of thestructures shown

Imine Bonding

In some embodiments, the reversible adhesive includes pH reversibleadhesives, such as reversible bonds produced by imine or iminium bonds.In some embodiments, the imine bonds are formed using any of thereversible adhesive backbone materials described herein, such asacrylic, methacrylic, derivatives thereof, or combinations thereof. Thereversible adhesive can be formed at a pH range of about 4 pH to about11 pH, such as a pH of about 5 to about 10, such as about 6 to about 8.The reversible adhesive can be reversed at pH below 4 or a pH above 7,such as a pH of about 1 to 2, or about 2 to about 3, or about 3 to about4, or about 7 to about 8, or about 8 to 9, or about 9 to 10, or about 11to 12, or about 12 to about 13, or about 13 to about 14. Upon reversalof the reversible adhesive, the reversible adhesive can form an amineand an aldehyde or a ketone. In some embodiments, the imine bond (alsoreferred to herein as imine linkage) is formed from a polymer backbonefunctionalized with an aldehyde moiety, such as dextran aldehydecrosslinked with an amine or an aniline compound or moiety. In someembodiments, aldehyde-amine bonds are formed between branched polyamineand p-formylphenyl acrylate.

In some embodiments, the reversible adhesive bonds can include other pHsensitive bonds, such as thiol groups or other pH sensitive groupsdescribed herein. Other pH sensitive bonds include ketals that arelabile in acidic environments, disulfides, acetals,silicon-oxygen-carbon linkages, silicon-nitrogen linkages, such assilazanes, silicon-carbon linkages, such as arylsilane, vinylsilanes,and allylsilanes, maleamates-amide bonds, ortho esters, hydrazones,activated carboxylic acid derivatives, acylhydrazones, oximes,benzoxaboroles, and combinations thereof.

In some embodiments, the reversible adhesive is prepared by reacting anamine functionalized polybutadiene with an aldehyde crosslinker to forma recyclable polybutadiene elastomer crosslinked by imine bonds. Theamine groups can be grafted onto the polybutadiene via a thiol-enereaction to form polybutadiene-NH2 which can be crosslinked withbenzene-1,3,5-tricarbaldehyde. The reversible adhesive can have ayoung's modulus of about 1 MPa to about 32 MPa, such as about 2 MPa toabout 10 MPa.

In some embodiments, an imine bond is formed by a condensation reactionof a ketone group, an aldehyde group, an acyl group, and an amino groupcontained in a compound. In some embodiments, the imine bond isintroduced into a polymer by polymerization or crosslinking reactionbetween reactive compounds that contain an imine bond. Reactivecompounds that include imine bonds include a polyol having an iminegroup, a polythiol having an imine group, a polyethyleneimine, apolyamine, an isocyanate, an epoxy compound having an imine group, analkene having an imine group, an alkyne having an imine group, orcombinations thereof.

The reversible adhesive can be reversed by altering the pH outside ofthe formation range. Without being bound by theory, it is believed thata change in pH alters a solubility of the polymer having the imine oriminium bonds. In some embodiments, the apparel products having thereversible bonds can be submerged in a solution having a pH outside ofthe pH range at which the reversible adhesive is formed. The pH of thesolution can be tuned, altered, or buffered by adding one or more ofcarboxylic acids, imidazole, pyridine, phenols, polyamines, orcombinations thereof. In some embodiments, the solution includes anacid-base catalyst including one or more of an inorganic acid, organicacid, and acid salt catalyst thereof. Inorganic acids include sulfuricacid, hydrochloric acid, phosphoric acid, or combinations thereof.Organic acids include methanesulfonic acid, benzenesulfonic acid,p-toluenesulfonic acid, and combinations thereof. Salt catalysts includesulfate, hydrogen sulfate, and hydrogen phosphate. The reversibleadhesive formation and reversal can occur at ambient conditions, such asa temperature of about 16° C. to about 35° C., such as about 18° C. toabout 26° C. In some embodiments, the apparel product is submerged forabout 1 second to about 1 hour, such as about 10 seconds to about 10minutes, such as about 30 seconds to about 50 minutes.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In a particular example synthesis of the reversible adhesive, a solutioncan be prepared by combining p-hydroxybenzaldehyde (e.g., 5 g, 41 mmol),triethylamine (6.5 mL), and dichloromethane (DCM) (50 mL). Acryloylchoride (4.5 g, 50 mmol) can be dissolved in 10 mL of DCM and addeddropwise to the solution. The reaction carried out in room temperaturefor about 12 hours. The trimethylamine hydrochloride was removed byfiltration, extracted with saturated NaHCO₃, and the organic phase wasdried with Na₂SO₄ and the p-formylphenyl acrylate was collected byrotary evaporation.

The extracted p-formylphenyl acrylate was combined with 100 mL ofmethanol and 10 g, 112 mmol branched polyamine PA_(6N) to form a secondsolution. Branched polyamines can be formed from reacting methylacrylate with an amine selected from ethylenediamine,diethylenetriamine, tris(2-aminoethyl)amine, triethylenetetramine,tetraethylenepentamine, or combinations thereof. PA_(6N) can be formedfrom triethylenetetramine. The second solution can be heated and areaction can occur over about 12 hours. A composition is collected byrotary evaporation. The molar ratio of polyamine to p-formylphenylacrylate can be about 1:5 to about 1:2, such as about 1:4 to about 2:5.

The composition is cured at a temperature of about 0° C. to about 100°C., such as about 16° C. to about 30° C. to form the reversibleadhesive. The composition can be deposited on a portion of the majorcomponent or a portion of the minor component. The major component andthe minor component can be coupled together via the composition. Thecomposition can be cured with or without the presence of pressure. Insome embodiments a pressure of about 1 kPa to about 10 kPa, such asabout 3 kPa to about 7 kPa can be applied between the components. Thecomposition can be cured in about 12 hours to about 36 hours, such asabout 18 hours to about 24 hours.

Shape Memory Materials

In some embodiments, the reversible adhesives are reversible uponexposure to light, such as ultraviolet light or heat. In someembodiments, the reversible adhesive is at least partially composed of ashape memory material, such as azobenzene, spiropyran, or combinationsthereof incorporated into one or more polymers described relative to thepolymer backbone materials described herein. In some embodiments, thereversible adhesive includes one or more of the polymer backbonematerials described herein, such as acrylic or methacrylic acidmonomers, derivatives thereof (e.g., esters and amides) thereof. In someembodiments, the reversible adhesive further includes light emittingmaterial, such as electroluminescence particles. In some embodiments,the reversible adhesive includes a conductive material. The conductivematerial is configured to convey electricity to the light emittingmaterial which illuminates upon application of the electricity. Thelight emitted from the light emitting material can deactivate the bondsof the shape memory material to reverse the adhesion of the reversibleadhesive.

In some embodiments, the conductive material is a carbon nanomaterial, asilver nanomaterial, a conductive metal, or combinations thereof. Insome embodiments, the conductive material is present in the reversibleadhesive in an amount of about 1 wt. % to about 90 wt. %, such as about10 wt. % to about 80 wt. %, such as about 20 wt. % to about 70 wt. %,such as about 30 wt. %. In some embodiments, the light emitting materialis present in the reversible adhesive in an amount of about 1 wt. % toabout 90 wt. %, such as about 10 wt. % to about 80 wt. %, such as about20 wt. % to about 70 wt. %, such as about 30 wt. %. The shape memorymaterial is configured to liquefy when exposed to a light having awavelength of about 100 nm to about 600 nm, such as about 300 nm toabout 400 nm.

Alternatively, the reversible adhesive can include any of the backbonepolymers described herein and the backbone polymer can be impregnated ordoped with shape memory materials, such as a plurality of linearlyshaped or oriented shape memory materials to conform to the surface ofthe component on which the reversible adhesive is applied. Duringdisassembly of the apparel products, a heat is applied to the reversibleadhesive which restores the shape memory to its original shape that isthree dimensional and is random relative to the surface of the componenton which the reversible adhesive is applied. The heat can be localizedto the reversible adhesive using the methods described herein relativeto particles (e.g., 204 shown in FIG. 2 ). In some embodiments, thereversible adhesive includes the shape memory materials in an amount ofabout 1 wt. % to about 90 wt. %, such as about 10 wt. % to about 80 wt.%, such as about 20 wt. % to about 70 wt. %, such as about 30 wt. %.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

In some embodiments, the reversible adhesive includes a metal includinggold/cadmium alloy, titanium/nickel alloy, copper/aluminum alloy, andthe like, and a shape memory polymer including polyurethane,polyethylene, epoxy, polystyrene, or combinations thereof.

In some embodiments, the shape memory material can be a plurality ofparticles, the particles having an average longest dimension of about 20μm to about 500 μm, such as about 50 μm to about 400 μm, such as about100 μm to about 300 μm.

An example shape memory material can be formed by mixing Poly(BisphenolA-co-epichlorohydrin), glycidyl end capped with a molecular weight of1075 g/mol, and a liquid bisphenol A based epoxy resin. The mixture ispreheated at a temperature of about 120° C. After heating, D-230poly(propylene glycol)bis(2-aminopropyl) ether with an average molecularweight of 230 g/mol is mixed into the preheated mixture to form a shapememory precursor. The shape memory precursor can be molded and cured at120° C. to a predetermined shape based on the shape of the mold. Thecured shape memory can be removed from the mold. The cured shape memorycan be coupled to the major component or the minor component via anadhesive material.

Epoxy based shape memory materials can include an elastic modulus ofabout 2.5 GPa to about 10 GPa.

In some embodiments, the reversible adhesive is reversed by heating at atemperature of about 80° C. or greater, such as about 90° C. to about200° C., such as about 100° C. to about 120° C., such as about 140° C.to about 160° C. The reversible adhesive can be exposed to heat orelectromagnetic energy for about 1 second to about 24 hours, such asabout 5 seconds to about 5 hours, such as about 1 minute to about 90minutes, such as about 30 minutes to about 60 minutes.

Cyclodextrin Bonding

In some embodiments, the reversible adhesive are reversible uponexposure to light, such as ultraviolet light. The backbone can includeany of the polymer backbone materials described herein, such as acrylicor methacrylic acid monomers, derivatives thereof (e.g., esters andamides) thereof. In some embodiments, the reversible adhesive includesacrylamide, acrylic acid, methyl acrylate, and 2-hydroxyethylmethacrylate. In some embodiments, the reversible adhesive is disposedon a portion of the apparel product and the portion can includestretchable fabric. The stretchable fabric can be stretched to increasearea of exposure to enable penetration of light to reverse bonds.

The reversible adhesive can be formed from a first monomer having acyclodextrin moiety, such as α-cyclodextrin, β-cyclodextrin,γ-cyclodextrin, and combinations thereof. The cyclodextrin can be bondedwith a monomer having an azobenzene moiety. In some embodiments, thecyclodextrin is non-covalently and reversibly bonded to the azobenzene.

The reversible adhesive can be formed from a second monomer includingthe azobenzene moiety. The second comonomer can include a vinyl monomersubstituent and additional groups such as alkyl groups that may have asubstituent or substituents, cycloalkyl groups, and aryl groups that mayhave a substituent or substituents. Examples of the alkyl group of theoptionally substituted alkyl group include linear, branched, or cyclicalkyl groups of C₁, to C₁₈, such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert butyl, pentyl, cyclopentyl, hexyl,cyclohexyl, isohexyl, dodecyl, octadecyl, and adamantyl. The alkyl groupmay have 1 to 3 substituents, for example, such as halogen atoms (forexample, such as fluorine, chlorine, and bromine), carboxyl groups,ester groups, amide groups, and hydroxyl groups that may be protected.In some embodiments, the monomer including the azobenzene moiety isdi(1-azobenzenemethyleketone))-1,2-bis(4-pyridyl)ethylene.

In some embodiment, the molar ratio of the monomer includingcyclodextrin to the monomer including azobenzene is about 60:1 to about1:60, such as about 30:1 to about 20:1, or about 10:1 to about 1:1, suchas about 8:1 to about 3:1, or about 1:10 to about 1:8, such as about 1:6to about 1:3. In some embodiments, the reversible adhesive can be formedusing a third monomer having adhesive properties, such as butyl acrylateor ethyl hexyl acrylate. The reversible adhesive can be formed fromthree monomers, the first monomer including cyclodextrin to the secondcomonomer including azobenzene can have a ratio of about 2:1 to about1:2, such as about 1:1.

In some embodiments, the reversible adhesive includes a reaction productof photopolymerization initiators, such as benzophenone,2,2-dimethoxy-1,2-diphenylethan-1-one, or combinations thereof. In someembodiments, the reversible adhesive can be applied on a component ofthe apparel product using any of the methods provided herein, such aspatterning the adhesive using photolithography or by nozzle deposition.In some embodiments, the reversible adhesive is applied to one of theportions of a first component (e.g., minor component) to be attached toone of the portions of a second component (e.g., major component).Alternately, the reversible adhesive can be applied to both the firstand second components.

The reversible adhesive can be cured by exposure to a first light havinga first wavelength, such as ultraviolet light or visible light. In someembodiment, a compressive pressure is applied to the first and secondcomponent for a predetermined time after the UV light exposure until thereversible adhesive is cured, such as about 1 second to about 1 hour,such as about 10 seconds to about 10 minutes, such as about 30 secondsto about 50 minutes.

In some embodiments, the reversible adhesive can be reversed by exposureto a second light having a second wavelength different from the firstwavelength used to cure the reversible adhesive, such as ultravioletlight or visible light. In some embodiments, the first light is visiblelight and the second light is ultraviolet light. In some embodiments,the intensity of the light exposure is greater than an intensityprovided in outdoor conditions under sunlight. In some embodiments, thelight intensity used to reverse the reversible adhesive is about 100mW/cm² to about 10,000 mW/cm², such as about 800 mW/cm² to about 8,000mW/cm², such as about 2,000 mW/cm² to about 6,000 mW/cm², such as about4,000 mW/cm² to about 5,000 mW/cm². In some embodiments, the light usedto reverse the reversible adhesive is a polarized light. The reversibleadhesive can be reversed after exposure to the second light for about 1minute to about 24 hours, such as about 10 minutes to about 20 hours,such as about 1 hour to about 6 hours.

In some embodiments, the reversible adhesive can include antioxidants orUV protectants configured to protect the reversible adhesive fromreversing in ambient conditions, such as normal sun exposure.

In some embodiments, the reversible adhesive can have a T-peel strengthof about 5 N/cm-width to about 100 N/cm-width, such as about 10N/cm-width to about 50 N/cm-width, such as about 20 N/cm-width to about30 N/cm-width, as tested according to ASTM D1876 (2015).

In some embodiments, the reversible adhesive includes multiple layerssuch as a primer layer disposed between the component of the apparelproduct and an adhesive layer that includes the reversible bonds.

In some embodiments, the reversible adhesive includes a gel having6-acrylamide-β-cyclodextrin-derived units andN-(1-adamantyl)acrylamide-derived units at a ratio of the6-acrylamide-β-cyclodextrin-derived units to theN-(1-adamantyl)acrylamide-derived units of 0.3:0.4.

In some embodiments, the reversible adhesive includes a gel preparedfrom hyaluronic acid polymers functionalized with a photoresponsive bondbetween a cyclodextrin and azobenzene. Upon exposure to light, thestorage modulus decreases by about 20% to about 60%, such as about 30%to about 40%.

In some embodiments, the reversible adhesive has a modulus of about 3mPa to about 3500 MPa, such as about 10 mPa to about 3000 MPa, such asabout 50 mPa to about 1500 mPa, such as about 90 mPa to about 125 mPa,according to tensiometric analysis using 100 N force and rate of 100mm/min. In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer has a glass transition temperature(T_(g)) of about −20° C. to about 200° C., such as about −10° C. toabout 100° C., such as 10° C. to about 20° C. In some embodiments, priorto crosslinking a polymer to form the reversible adhesive, the polymerhas a melting temperature (T_(m)) of about 75° C. to about 200° C., suchas 100° C. to about 175° C., such as about 125° C. to about 150° C.

In some embodiments, prior to crosslinking a polymer to form thereversible adhesive, the polymer can have a molecular weight (e.g.,weight average molecular weight) of about 700 g/mol to about 1,000,000g/mol, such as about 1,000 g/mol to about 500,000 g/mol, such as about10,000 g/mol to about 250,000 g/mol. The reversible adhesive aftercrosslinking can have polymer(s) having a much higher molecular weightthan before crosslinking because, after crosslinking, multiple polymermolecules are crosslinked together.

In some embodiments, the reversible adhesive includes a first viscosityand a first solubility in a solvent. The reversible adhesive aftertreating the reversible adhesive with a deactivating condition has asecond viscosity. The second viscosity can be less than the firstviscosity, such as about 10% to about 99% less, such as about 20% toabout 90% less, such as about 40% to about 80% less, such as about 60%to about 75% less. The reversible adhesive after treating the reversibleadhesive can have a second solubility higher than the first solubilityin a solvent. In some embodiments, the reversible adhesive beforetreating is not soluble in a solvent, such as an organic solvent, andthe reversible adhesive after treating is soluble in the solvent (at thesame temperature and pressure conditions as that of the reversibleadhesive before treating).

The reversible adhesive used to join components can include a mixture ofone or more of the reversible adhesives described herein, such as atemperature reversible adhesive (such as a Diels-Alder reversibleadhesive), a chemical reversible adhesive (such as disulfide reversibleadhesive), a thioester reversible adhesive, a boronic acid reversibleadhesive, imine reversible adhesive, light reversible adhesive (such ascyclodextrin-azobenzene reversible adhesive), shape memory reversibleadhesive.

Overall, a number of different chemistries can be incorporated into thereversible adhesive to provide controlled disassembling of the productsin a streamlined large-scale process. The apparel products describedherein can include a number of different components that can be joinedtogether by the reversible adhesive and separated from one another usingthe methods described herein depending on the composition of the apparelproduct components.

Additional Aspects

The present disclosure can include the following non-limiting aspectsand/or embodiments:

Clause A1. A method of disassembling an apparel product, comprising:exposing an adhesive of the apparel product to electromagnetic energy,the adhesive being disposed at least partially between a major componentand a minor component of the apparel product, the adhesive comprising apolymer having a cyclodextrin moiety bonded to an azobenzene moiety, themajor component forming a base portion of the apparel product andconfigured to be supported and worn at least partially over a portion ofa wearer, and the minor component forming a secondary portion configuredto be coupled to the major component with the adhesive; and separatingthe major component from the minor component adjoined by the adhesive.

Clause A2. The method of Clause A1, wherein the cyclodextrin moiety isselected from the group consisting of an α-cyclodextrin, aβ-cyclodextrin, a γ-cyclodextrin, and combinations thereof.

Clause A3. The method of Clause A1 or Clause A2, wherein thecyclodextrin moiety is non-covalently bonded to the azobenzene moiety.

Clause A4. The method of any of Clauses A1 to A3, wherein the adhesivefurther comprises a light emitting material and a conductive material,wherein exposing the apparel product to electromagnetic energy comprisesproviding electricity to the conductive material and illuminating thelight emitting material.

Clause A5. The method of any of Clauses A1 to A4, wherein exposing theadhesive to the electromagnetic energy comprises exposing the adhesiveto a light having a light intensity of about 800 mW/cm² to about 10,000mW/cm².

Clause A6. The method of any of Clauses A1 to A4, wherein the apparelproduct is selected from the group consisting of a shirt, a pant, askirt, a coat, a dress, a sweater, a body suit, and combinationsthereof.

Clause A7. The method of any of Clauses A1 to A6, wherein the majorcomponent comprises a material selected from a polyester, a polyamide, acotton, mixtures thereof, and combinations thereof.

Clause A8. The method of any of Clauses A1 to A7, wherein the adhesivehas a T-peel strength of about 5 N/cm to about 100 N/cm.

Clause A9. The method of any of Clauses A1 to A8, wherein the azobenzenemoiety is bonded to a monomeric unit of the polymer, the monomeric unitselected from the group consisting of an acrylamide, an acrylic acid, amethyl acrylate, a 2-hydroxyethyl methacrylate, and combinationsthereof.

Clause A10. The method of any of Clauses A1 to A9, wherein theazobenzene moiety is bonded to a monomeric unit, the monomeric unitfurther comprising a substituent selected from the group consisting of amethyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, an isobutyl, asec-butyl, a tert butyl, a pentyl, a cyclopentyl, a hexyl, a cyclohexyl,an isohexyl, a dodecyl, an octadecyl, an adamantyl, and combinationsthereof.

Clause A11. The method of any of Clauses A1 to A11, wherein theelectromagnetic energy is a light having a wavelength of about 100 nm toabout 400 nm.

Clause A12. The method of any of Clauses A1 to A11, further comprisingsorting the separated major component and the minor component.

Clause A13. The method of any of Clauses A1 to A12, further comprisingseparating a second minor component from the major component.

Clause A14. The method of any of Clauses A1 to A13, further comprisingseparating the adhesive from the major component or the minor component,further comprising applying a centrifugal force to the apparel productat a rotational speed of about 500 rpm to about 1,000 rpm.

Clause A15. The method of any of Clauses A1 to A14, wherein the polymercomprises a first monomeric unit comprising the cyclodextrin moietynon-covalently bonded to a second monomeric unit comprising theazobenzene moiety, wherein exposing the adhesive to the electromagneticenergy weakens the non-covalent bond between the first and secondmonomeric unit.

Clause A16. A method of disassembling an apparel product, comprising:exposing an adhesive comprising a polymer having a cyclodextrin moietybonded to an azobenzene moiety to an electromagnetic energy, theadhesive being disposed at least partially between a major component anda minor component of the apparel product, wherein the compositionweakens bonding between the main component and the minor component, themajor component forming a base portion of the apparel product andconfigured to be supported and worn at least partially over a portion ofa wearer, and the minor component forming a secondary portion configuredto be coupled to the major component with the adhesive; and separatingthe major component from the minor component adjoined by the adhesive,the major component comprising synthetic or natural fibers, wherein themajor component or minor component comprises recyclable material.

Clause A17. The method of Clause A16, further comprising separating theadhesive from the major component or the minor component, whereinseparating comprises applying a centrifugal force to the apparel productfor about 1 minute to about 30 minutes.

Clause A18. The method of Clause A16 or Clause A17, wherein exposing theadhesive to the electromagnetic energy comprises stretching the majorcomponent or the minor component on either side of the adhesive andexposing the stretched major component or minor component to a light.

Clause A19. The method of any of Clauses A16 to A18, wherein the polymercomprises a first monomeric unit comprising the cyclodextrin moietynon-covalently bonded to a second monomeric unit comprising theazobenzene moiety.

Clause A20. A method of disassembling apparel products, the methodcomprising: exposing a plurality of apparel products to electromagneticenergy, each apparel product of the plurality of apparel products havingan adhesive comprising a polymer having a cyclodextrin moiety bonded toan azobenzene moiety disposed between a major component and a minorcomponent of each apparel product of the plurality of apparel products,each of the major components forming a base portion of the apparelproduct and configured to be supported and worn at least partially overa portion of a wearer, and each of the minor components forming asecondary portion configured to be coupled to a respective majorcomponent with the adhesive; an applying a centrifugal force to theplurality of apparel products.

Clause B1. A method of assembling an apparel product, comprising:applying a composition to a portion of a major component of the apparelproduct or a portion of a minor component of the apparel product;coupling the portion of the minor component with the portion of themajor component via the composition, the major component forming a baseportion of the apparel product and configured to be supported and wornat least partially over a portion of a wearer, and the minor componentforming a secondary portion configured to be coupled to the majorcomponent with an adhesive; and curing the composition to form theadhesive and the apparel product, the adhesive comprising a polymerhaving a cyclodextrin moiety bonded to an azobenzene moiety.

Clause B2. The method of Clause B1, wherein the cyclodextrin moiety isselected from the group consisting of an α-cyclodextrin, aβ-cyclodextrin, a γ-cyclodextrin, and combinations thereof.

Clause B3. The method of Clause B1 or Clause B2, wherein thecyclodextrin moiety is non-covalently bonded to the azobenzene moiety.

Clause B4. The method of any of Clauses B1 to B3, further comprisingintroducing a light emitting material and a conductive material to thecomposition or the adhesive.

Clause B5. The method of any of Clauses B1 to B4, wherein curing thecomposition comprises exposing the composition to a visible light.

Clause B6. The method of any of Clauses B1 to B5, wherein curing thecomposition further comprises curing at a temperature of about 16° C. toabout 35° C.

Clause B7. The method of any of Clauses B1 to B6, wherein thecomposition is applied such that the adhesive has a thickness of about0.025 mm to about 5 mm.

Clause B8. The method of any of Clauses B1 to B7, wherein curing thecomposition comprises exposing the composition to an ultraviolet light.

Clause B9. The method of any of Clauses B1 to B8, wherein curing thecomposition comprises applying a force by pressing the portion of themajor component against the portion of the minor component.

Clause B10. A method of assembling an apparel product, comprising:applying a composition to a portion of a major component of the apparelproduct or a portion of a minor component of the apparel product; dopingthe composition with particles after applying the composition to theportion of the major component or the portion of the minor product;coupling the portion of the minor component with the portion of themajor component via the composition, the major component forming a baseportion of the apparel product and configured to be supported and wornat least partially over a portion of a wearer, and the minor componentforming a secondary portion configured to be coupled to the majorcomponent with an adhesive; and curing the composition to form theadhesive and the apparel product, the adhesive comprising a polymerhaving a cyclodextrin moiety bonded to an azobenzene moiety.

Clause B11. The method of Clause B10, wherein applying the compositioncomprises patterning the composition by a photolithography process.

Clause B12. The method of Clause B10 or Clause B11, wherein theparticles comprise electroluminescence particles.

Clause B13. The method of any of Clauses B10 to B12, further comprisingforming the composition from a first monomer having a cyclodextrinmoiety and a second monomer having an azobenzene moiety, wherein a molarratio of the first monomer to the second monomer is about 1:3 to about3:1.

Clause B14. The method of any of Clauses B10 to B13, wherein thecomposition is at least partially incorporated into the portion of themajor component or the minor component.

Clause B15. A method of assembling an apparel product, comprising:applying a composition to a portion of a major component of the apparelproduct or a portion of the minor component of the apparel product;coupling the portion of the minor component with the portion of themajor component via the composition, the major component forming a baseportion of the apparel product and configured to be supported and wornat least partially over a portion of a wearer, and the minor componentforming a secondary portion configured to be coupled to the majorcomponent with an adhesive comprising a polymer having a cyclodextrinmoiety bonded to a cyclic azobenzene moiety; and curing the compositionto form the adhesive and the apparel product.

Clause B16. The method of Clause B15, wherein the azobenzene moiety isbonded to a monomeric unit, the monomeric unit further comprising asubstituent selected from the group consisting of a methyl, an ethyl, ann-propyl, an isopropyl, an n-butyl, an isobutyl, a sec-butyl, a tertbutyl, a pentyl, a cyclopentyl, a hexyl, a cyclohexyl, an isohexyl, adodecyl, a octadecyl, an adamantyl, and combinations thereof.

Clause B17. The method of Clause B15 or Clause B16, further comprisingforming the composition from a first monomer having a cyclodextrinmoiety, a second monomer having an azobenzene moiety, and a thirdmonomer.

Clause B18. The method of any of Clauses B15 to B17, wherein the majorcomponent or the minor component comprises a stretchable material.

Clause B19. The method of any of Clauses B15 to B18, wherein thestretchable material comprises a polyether-polyurea copolymer.

Clause B20. The method of any of Clauses B15 to B19, wherein theadhesive further comprises a conductive material.

Clause C1. An apparel product, comprising: a major component forming abase portion of the apparel product and configured to be supported andworn at least partially over a portion of a wearer; a minor componentforming a secondary portion configured to be coupled to the majorcomponent; and an adhesive disposed between a portion of the majorcomponent and a portion of the minor component, the adhesive comprisinga polymer having a cyclodextrin moiety bonded to an azobenzene moiety.

Clause C2. The apparel product of Clause C1, wherein the apparel productis selected from the group consisting of a shirt, a pant, a skirt, acoat, a dress, a sweater, a body suit, and combinations thereof.

Clause C3. The apparel product of Clause C1 or C2, wherein the majorcomponent comprises a material selected from a polyester, a polyamide, acotton, mixtures thereof, and combinations thereof.

Clause C4. The apparel product of any of Clauses C1 to C3, wherein theadhesive has a thickness of about 0.025 mm to about 5 mm.

Clause C5. The apparel product of any of Clauses C1 to C4, wherein theadhesive comprises electroluminescence particles.

Clause C6. The apparel product of any of Clauses C1 to C5, wherein themajor or minor component comprises a polyether-polyurea copolymer.

Clause C7. The apparel product of any of Clauses C1 to C6, wherein thecyclodextrin moiety is non-covalently bonded to the azobenzene moiety.

Clause C8. The apparel product of any of Clauses C1 to C7, wherein theadhesive has a T-peel strength of about 5 N/cm to about 100 N/cm.

Clause C9. The apparel product of any of Clauses C1 to C8, wherein themajor component or the minor component is composed of a recyclablematerial.

Clause C10. An apparel product, comprising: a major component of theapparel product, the major component forming a base portion of theapparel product and configured to be supported and worn at leastpartially over a portion of a wearer; a minor component of the apparelproduct forming a secondary portion configured to be coupled to themajor component; and an adhesive disposed on a portion of the majorcomponent or the minor component of the apparel product, the adhesivecomprising: a polymer comprising a cyclodextrin moiety bonded to anazobenzene moiety; and a plurality of particles.

Clause C11. The apparel product of Clause C10, wherein the polymercomprises monomeric units selected from the group consisting of anacrylate, a methacrylate, an acrylic, an ethylene, a propylene, astyrene, a vinyl acetate, a vinyl ester monomer, and combinationsthereof.

Clause C12. The apparel product of Clause C10 or C11, wherein theplurality of particles comprises electroluminescence particles.

Clause C13. The apparel product of any of Clauses C10 to C12, whereinthe adhesive further comprises a conductive material selected from thegroup consisting of gold, cadmium, titanium, nickel, copper, aluminum,alloys thereof, and combinations thereof.

Clause C14. The apparel product of any of Clauses C10 to C13, whereinthe cyclodextrin moiety is selected from the group consisting of anα-cyclodextrin, a β-cyclodextrin, a γ-cyclodextrin, and combinationsthereof.

Clause C15. An apparel product, comprising: a major component forming abase portion of the apparel product and configured to be supported andworn at least partially over a portion of a wearer, the major componentcomprising a first polymer; a minor component forming a secondaryportion configured to be coupled to the major component, the minorcomponent comprising a second polymer; and an adhesive disposed on aportion of the major component or the minor component of the apparelproduct, the adhesive comprising a third polymer, the third polymerhaving a cyclodextrin moiety bonded to a azobenzene moiety.

Clause C16. The apparel product of Clause C15, wherein the cyclodextrinmoiety is non-covalently bonded to the azobenzene moiety.

Clause C17. The apparel product of Clause C15 or Clause C16, wherein theadhesive further comprises a tackifier.

Clause C18. The apparel product of any of Clauses C15 to C17, whereinthe adhesive further comprises a polyurethane matrix, wherein the thirdpolymer is incorporated into the polyurethane matrix.

Clause C19. The apparel product of any of Clauses C15 to C18, whereinthe third polymer comprises a first monomeric unit having a cyclodextrinmoiety and a second monomeric unit having an azobenzene moiety, whereina molar ratio of the first monomeric unit to the second monomeric unitis about 1:3 to about 3:1.

Clause C20. The apparel product of any of Clauses C15 to C19, whereinthe azobenzene moiety is bonded to a monomeric unit, the monomeric unitcomprising a substituent selected from the group consisting of a methyl,an ethyl, an n-propyl, an isopropyl, an n-butyl, an isobutyl, asec-butyl, a tert butyl, a pentyl, a cyclopentyl, a hexyl, a cyclohexyl,an isohexyl, a dodecyl, a octadecyl, an adamantyl, and combinationsthereof.

In the current disclosure, reference is made to various embodiments.However, it should be understood that the present disclosure is notlimited to specific described embodiments. Instead, any combination ofthe following features and elements, whether related to differentembodiments or not, is contemplated to implement and practice theteachings provided herein. Additionally, when elements of theembodiments are described in the form of “at least one of A and B,” itwill be understood that embodiments including element A exclusively,including element B exclusively, and including element A and B are eachcontemplated. Furthermore, although some embodiments may achieveadvantages over other possible solutions or over the prior art, whetheror not a particular advantage is achieved by a given embodiment is notlimiting of the present disclosure. Thus, the aspects, features,embodiments and advantages disclosed herein are merely illustrative andare not considered elements or limitations of the appended claims exceptwhere explicitly recited in a claim(s).

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the disclosure may bedevised without departing from the basic scope thereof, and the scopethereof is determined by the claims that follow.

What is claimed is:
 1. A method of disassembling an apparel product,comprising: exposing an adhesive of the apparel product toelectromagnetic energy, the adhesive being disposed at least partiallybetween a major component and a minor component of the apparel product,the adhesive comprising a polymer having a cyclodextrin moiety bonded toan azobenzene moiety, the major component forming a base portion of theapparel product and configured to be supported and worn at leastpartially over a portion of a wearer, and the minor component forming asecondary portion configured to be coupled to the major component withthe adhesive; and separating the major component from the minorcomponent adjoined by the adhesive.
 2. The method of claim 1, whereinthe cyclodextrin moiety is selected from the group consisting of anα-cyclodextrin, a β-cyclodextrin, a γ-cyclodextrin, and combinationsthereof.
 3. The method of claim 1, wherein the cyclodextrin moiety isnon-covalently bonded to the azobenzene moiety.
 4. The method of claim1, wherein the adhesive further comprises a light emitting material anda conductive material, wherein exposing the apparel product toelectromagnetic energy comprises providing electricity to the conductivematerial and illuminating the light emitting material.
 5. The method ofclaim 1, wherein exposing the adhesive to the electromagnetic energycomprises exposing the adhesive to a light having a light intensity ofabout 800 mW/cm² to about 10,000 mW/cm².
 6. The method of claim 1,wherein the apparel product is selected from the group consisting of ashirt, a pant, a skirt, a coat, a dress, a sweater, a body suit, andcombinations thereof.
 7. The method of claim 1, wherein the majorcomponent comprises a material selected from a polyester, a polyamide, acotton, and combinations thereof.
 8. The method of claim 1, wherein theadhesive has a T-peel strength of about 5 N/cm to about 100 N/cm.
 9. Themethod of claim 1, wherein the azobenzene moiety is bonded to amonomeric unit of the polymer, the monomeric unit selected from thegroup consisting of an acrylamide, an acrylic acid, a methyl acrylate, a2-hydroxyethyl methacrylate, and combinations thereof.
 10. The method ofclaim 1, wherein the azobenzene moiety is bonded to a monomeric unit,the monomeric unit further comprising a substituent selected from thegroup consisting of a methyl, an ethyl, an n-propyl, an isopropyl, ann-butyl, an isobutyl, a sec-butyl, a tert butyl, a pentyl, acyclopentyl, a hexyl, a cyclohexyl, an isohexyl, a dodecyl, anoctadecyl, an adamantyl, and combinations thereof.
 11. The method ofclaim 10, wherein the electromagnetic energy is a light having awavelength of about 100 nm to about 400 nm.
 12. The method of claim 1,further comprising sorting the separated major component and the minorcomponent.
 13. The method of claim 1, further comprising separating asecond minor component from the major component.
 14. The method of claim1, further comprising separating the adhesive from the major componentor the minor component, further comprising applying a centrifugal forceto the apparel product at a rotational speed of about 500 rpm to about1,000 rpm.
 15. The method of claim 14, wherein the polymer comprises afirst monomeric unit comprising the cyclodextrin moiety non-covalentlybonded to a second monomeric unit comprising the azobenzene moiety,wherein exposing the adhesive to the electromagnetic energy weakens thenon-covalent bond between the first and second monomeric unit.
 16. Amethod of disassembling an apparel product, comprising: exposing anadhesive comprising a polymer having a cyclodextrin moiety bonded to anazobenzene moiety to an electromagnetic energy, the adhesive beingdisposed at least partially between a major component and a minorcomponent of the apparel product, in order to weaken a bonding strengthbetween the main component and the minor component, the major componentforming a base portion of the apparel product and configured to besupported and worn at least partially over a portion of a wearer, andthe minor component forming a secondary portion configured to be coupledto the major component with the adhesive; and separating the majorcomponent from the minor component adjoined by the adhesive, the majorcomponent comprising synthetic or natural fibers, wherein the majorcomponent or minor component comprises recyclable material.
 17. Themethod of claim 16, further comprising separating the adhesive from themajor component or the minor component, wherein separating the adhesivecomprises applying a centrifugal force to the apparel product for about1 minute to about 30 minutes.
 18. The method of claim 16, whereinexposing the adhesive to the electromagnetic energy comprises stretchingthe major component or the minor component on either side of theadhesive and exposing the stretched major component or minor componentto a light.
 19. The method of claim 16, wherein the polymer comprises afirst monomeric unit comprising the cyclodextrin moiety non-covalentlybonded to a second monomeric unit comprising the azobenzene moiety. 20.A method of disassembling apparel products, the method comprising:exposing a plurality of apparel products to electromagnetic energy, eachapparel product of the plurality of apparel products having an adhesivecomprising a polymer having a cyclodextrin moiety bonded to anazobenzene moiety disposed between a major component and a minorcomponent of each apparel product of the plurality of apparel products,each of the major components forming a base portion of the apparelproduct and configured to be supported and worn at least partially overa portion of a wearer, and each of the minor components forming asecondary portion configured to be coupled to a respective majorcomponent with the adhesive; and applying a centrifugal force to theplurality of apparel products.